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2020 Volume 39 Issue 8
2020, 39(8): 1363-1371
doi: 10.14102/j.cnki.0254–5861.2011–2920
Abstract:
Poor cycling stability, as a long-standing issue, has greatly hindered the commercial application of Li-rich layered oxide cathodes in high-energy-density Li-ion batteries. NiO-type rock-salt phase is commonly considered electrochemically inert but stable. Herein, an ultrathin (LixTM1-x)O rock-salt shell was in situ constructed at the particle surface during the synthesis of Li-rich layered oxide cathodes through a unique soft chemical quenching method. Comprehensive structural/chemical analysis reveals that, it not only inherits the chemical stability of traditional NiO-type rock-salt phase, but also facilitates Li+ diffusion due to the co-occupancy of Li+ and TM cations. Such a bifunctional shell could efficiently prevent TM dissolution and oxygen evolution during the long-term cycling, eventually leading to the enhanced cycling stability for Li-rich layered oxides (92.7% of capacity retention after 200 cycles at 0.5C). It provides new guidance to design and synthesize new Li-rich layered oxides with the excellent cycling stability through utilizing some electrochemically-inert phases.
Poor cycling stability, as a long-standing issue, has greatly hindered the commercial application of Li-rich layered oxide cathodes in high-energy-density Li-ion batteries. NiO-type rock-salt phase is commonly considered electrochemically inert but stable. Herein, an ultrathin (LixTM1-x)O rock-salt shell was in situ constructed at the particle surface during the synthesis of Li-rich layered oxide cathodes through a unique soft chemical quenching method. Comprehensive structural/chemical analysis reveals that, it not only inherits the chemical stability of traditional NiO-type rock-salt phase, but also facilitates Li+ diffusion due to the co-occupancy of Li+ and TM cations. Such a bifunctional shell could efficiently prevent TM dissolution and oxygen evolution during the long-term cycling, eventually leading to the enhanced cycling stability for Li-rich layered oxides (92.7% of capacity retention after 200 cycles at 0.5C). It provides new guidance to design and synthesize new Li-rich layered oxides with the excellent cycling stability through utilizing some electrochemically-inert phases.
2020, 39(8): 1372-1376
doi: 10.14102/j.cnki.0254–5861.2011–2918
Abstract:
Since the discovery of surface-enhanced Raman spectroscopy (SERS), it has been rapidly applied to the in situ study of electrochemical interfaces. Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) stands out as one of the most powerful tools for the in situ study of interfacial structures, especially on well-defined single crystal surface. This perspective paper focuses on the study of interfacial structures with the SHINERS technique, including the electronic structure of heterogeneous metal surfaces, and the detection of molecules absorbed on the surface, as well as intermediate species, during electrochemical reactions. Finally, we present an outlook on future research and development of SHINERS for studying interfacial structures.
Since the discovery of surface-enhanced Raman spectroscopy (SERS), it has been rapidly applied to the in situ study of electrochemical interfaces. Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) stands out as one of the most powerful tools for the in situ study of interfacial structures, especially on well-defined single crystal surface. This perspective paper focuses on the study of interfacial structures with the SHINERS technique, including the electronic structure of heterogeneous metal surfaces, and the detection of molecules absorbed on the surface, as well as intermediate species, during electrochemical reactions. Finally, we present an outlook on future research and development of SHINERS for studying interfacial structures.
2020, 39(8): 1377-1384
doi: 10.14102/j.cnki.0254–5861.2011–2944
Abstract:
On-surface synthesis never fails to fascinate chemists by producing new functional polymers which can hardly been prepared via traditional solution chemistry. Among those newly prepared polymers, graphene nanoribbons (GNRs), featured with tunable band gap, have attracted substantial attention because they are considered as promising candidates for next generation carbon-based semiconductors. Here, we summarize the recent advances of GNRs prepared on single crystal surfaces with emphasis on the structural tuning and electronic properties of GNRs. Moreover, critical developments toward the application of GNRs have also been reviewed including the mass fabrication and the performance of GNRs as field effect transistors.
On-surface synthesis never fails to fascinate chemists by producing new functional polymers which can hardly been prepared via traditional solution chemistry. Among those newly prepared polymers, graphene nanoribbons (GNRs), featured with tunable band gap, have attracted substantial attention because they are considered as promising candidates for next generation carbon-based semiconductors. Here, we summarize the recent advances of GNRs prepared on single crystal surfaces with emphasis on the structural tuning and electronic properties of GNRs. Moreover, critical developments toward the application of GNRs have also been reviewed including the mass fabrication and the performance of GNRs as field effect transistors.
2020, 39(8): 1385-1394
doi: 10.14102/j.cnki.0254–5861.2011–2611
Abstract:
Topomer comparative molecular field analysis (Topomer CoMFA) and holographic quantitative structure-activity relationship (HQSAR) for 130 2,5-diketopiperazine derivatives were used to build a three-dimensional quantitative structure-activity relationship (3D-QSAR) model. The results show that the models have high predictive ability. For Topomer CoMFA, the cross-validated q2 value is 0.710 and the non-cross-validated r2 value is 0.834. The most effective HQSAR model shows that the cross-validation q2 value is 0.700, the non-cross-validated r2 value is 0.815, and the best hologram length value is 353 using connections and bonds as fragment distinctions. 50 highly active 2,5-diketopiperazine derivatives were designed based on the three-dimensional equipotential map and HQSAR color code map. Finally, the molecular docking method was also used to study the interactions of these new molecules by docking the ligands into the diketopiperazine active site, which revealed the likely bioactive conformations. This study showed that there are extensive interactions between the new molecule and Arg156, Arg122 residues in the active site of diketopiperazine. These results provide useful insights for the design of potent of the new 2,5-diketopiperazine derivatives.
Topomer comparative molecular field analysis (Topomer CoMFA) and holographic quantitative structure-activity relationship (HQSAR) for 130 2,5-diketopiperazine derivatives were used to build a three-dimensional quantitative structure-activity relationship (3D-QSAR) model. The results show that the models have high predictive ability. For Topomer CoMFA, the cross-validated q2 value is 0.710 and the non-cross-validated r2 value is 0.834. The most effective HQSAR model shows that the cross-validation q2 value is 0.700, the non-cross-validated r2 value is 0.815, and the best hologram length value is 353 using connections and bonds as fragment distinctions. 50 highly active 2,5-diketopiperazine derivatives were designed based on the three-dimensional equipotential map and HQSAR color code map. Finally, the molecular docking method was also used to study the interactions of these new molecules by docking the ligands into the diketopiperazine active site, which revealed the likely bioactive conformations. This study showed that there are extensive interactions between the new molecule and Arg156, Arg122 residues in the active site of diketopiperazine. These results provide useful insights for the design of potent of the new 2,5-diketopiperazine derivatives.
2020, 39(8): 1395-1404
doi: 10.14102/j.cnki.0254–5861.2011–2622
Abstract:
With the aim of designing and preparing the materials based on polyoxometalates (POMs) and themetal-organic frameworks (MOFs) toward desired applications, a facile approach was developed to incorporate theclusters of Mo7O246- (Mo7), a representative isopolyoxometalate, into the vacant cages of ZIF-8. Through theso-called strategy of building MOF bottles around the POM ships, the powdered crystals and crystalline membraneof Mo7@ZIF-8 were synthesized, respectively. The products were characterized by IR, PXRD, N2 adsorption, andSEM. The Mo7@ZIF-8 crystals could effectively adsorb malachite green (MG) from water, and the maximumadsorption capacity reached 1963 mg·g-1. The Mo7@ZIF-8 crystals could also be used for selectively adsorbing MGfrom the mixed dye solution containing MG and methyl orange (MO). Moreover, the Mo7@ZIF-8 membraneexhibited the proton conductivity of 9.5 × 10-2 S·cm-1 at 75 ℃ under 98% relative humidity.
With the aim of designing and preparing the materials based on polyoxometalates (POMs) and themetal-organic frameworks (MOFs) toward desired applications, a facile approach was developed to incorporate theclusters of Mo7O246- (Mo7), a representative isopolyoxometalate, into the vacant cages of ZIF-8. Through theso-called strategy of building MOF bottles around the POM ships, the powdered crystals and crystalline membraneof Mo7@ZIF-8 were synthesized, respectively. The products were characterized by IR, PXRD, N2 adsorption, andSEM. The Mo7@ZIF-8 crystals could effectively adsorb malachite green (MG) from water, and the maximumadsorption capacity reached 1963 mg·g-1. The Mo7@ZIF-8 crystals could also be used for selectively adsorbing MGfrom the mixed dye solution containing MG and methyl orange (MO). Moreover, the Mo7@ZIF-8 membraneexhibited the proton conductivity of 9.5 × 10-2 S·cm-1 at 75 ℃ under 98% relative humidity.
2020, 39(8): 1405-1421
doi: 10.14102/j.cnki.0254–5861.2011–2449
Abstract:
A comprehensive density functional theory calculation was employed to investigate the possible reaction pathways and mechanisms of methane complete oxidation (CH4 + 2O2 → CO2 + 2H2O) on different manganese oxides including α-MnO2(100) and β-MnO2(111) surfaces. According to a coupling of the Mars-van Krevelen and Langmuir-Hinshelwood mechanism, the activation energy barrier and the reaction energy of each elementary surface reaction were determined. Our calculated results show that the detailed processes for methane oxidation on two surfaces are different due to the differences in the surface structure. The breaking of the last C–H bond of CH4 molecule is the rate-determining step with an activation barrier of 0.85 eV for α-MnO2(100) surface. By contrast, the overall reaction rate on β-MnO2(111) surface is limited by the dissociation of the second O2 molecule adsorbed on the vacancy site, and re-oxidation of the reduced β-MnO2(111) surface by the gaseous oxygen requires a much higher energy barrier of 1.44 eV. As a result, the α-MnO2(100) exhibits superior activity and durability in the methane oxidation reaction than β-MnO2(111) surface. The present study provides insight into understanding the structure-catalytic activity relationship of the catalysts based on manganese oxides towards the methane oxidation reaction.
A comprehensive density functional theory calculation was employed to investigate the possible reaction pathways and mechanisms of methane complete oxidation (CH4 + 2O2 → CO2 + 2H2O) on different manganese oxides including α-MnO2(100) and β-MnO2(111) surfaces. According to a coupling of the Mars-van Krevelen and Langmuir-Hinshelwood mechanism, the activation energy barrier and the reaction energy of each elementary surface reaction were determined. Our calculated results show that the detailed processes for methane oxidation on two surfaces are different due to the differences in the surface structure. The breaking of the last C–H bond of CH4 molecule is the rate-determining step with an activation barrier of 0.85 eV for α-MnO2(100) surface. By contrast, the overall reaction rate on β-MnO2(111) surface is limited by the dissociation of the second O2 molecule adsorbed on the vacancy site, and re-oxidation of the reduced β-MnO2(111) surface by the gaseous oxygen requires a much higher energy barrier of 1.44 eV. As a result, the α-MnO2(100) exhibits superior activity and durability in the methane oxidation reaction than β-MnO2(111) surface. The present study provides insight into understanding the structure-catalytic activity relationship of the catalysts based on manganese oxides towards the methane oxidation reaction.
2020, 39(8): 1422-1436
doi: 10.14102/j.cnki.0254–5861.2011–2473
Abstract:
In this research, a density functional theory (DFT) calculation was performed for investigation adsorption behavior of the anticancer drug Vemurafenib on BNNT(5,5-9) by using the M06-2X/6-31G* level of theory in the solvent water. The electronic spectra of the Vemurafenib drug, BNNT(5,5-9) and complex BNNT(5,5-9)/Vemurafenib in solvent water were calculated by Time Dependent Density Functional Theory (TD-DFT) for the study of adsorption effect. The non-bonded interaction effects of the Vemurafenib drug with BNNT(5,5-9) on the electronic properties, natural charges and chemical shift tensors have been also detected. The results display the change in title parameters after process adsorption. According to the natural bond orbital (NBO) results, the molecule Vemurafenib and BNNT(5,5-9) play as both electron donor and acceptor at the complex BNNT(5,5-9)/Vemurafenib. On the other hand, the charge transfer occurs between the bonding, antibonding or nonbonding orbitals in two molecules drug and BNNT. As a consequence, BNNT(5,5-9) can be considered as a drug delivery system for the transportation of Vemurafenib as anticancer drug within the biological systems.
In this research, a density functional theory (DFT) calculation was performed for investigation adsorption behavior of the anticancer drug Vemurafenib on BNNT(5,5-9) by using the M06-2X/6-31G* level of theory in the solvent water. The electronic spectra of the Vemurafenib drug, BNNT(5,5-9) and complex BNNT(5,5-9)/Vemurafenib in solvent water were calculated by Time Dependent Density Functional Theory (TD-DFT) for the study of adsorption effect. The non-bonded interaction effects of the Vemurafenib drug with BNNT(5,5-9) on the electronic properties, natural charges and chemical shift tensors have been also detected. The results display the change in title parameters after process adsorption. According to the natural bond orbital (NBO) results, the molecule Vemurafenib and BNNT(5,5-9) play as both electron donor and acceptor at the complex BNNT(5,5-9)/Vemurafenib. On the other hand, the charge transfer occurs between the bonding, antibonding or nonbonding orbitals in two molecules drug and BNNT. As a consequence, BNNT(5,5-9) can be considered as a drug delivery system for the transportation of Vemurafenib as anticancer drug within the biological systems.
2020, 39(8): 1437-1443
doi: 10.14102/j.cnki.0254–5861.2011–2612
Abstract:
In this paper, we report our attempts to raise the efficiency of liquid reduction method when using high specific surface area TiO2 (HSTiO2) by doping Au. Characterization of Au-HSTiO2 was conducted via XRD, UV-vis, SEM, and photocurrent intensity. The experimental results show that Au-HSTiO2 exhibits prominently higher photocatalytic hydrogen production than TiO2 and HSTiO2. Enhanced photosynthetic hydrogen production ability of Au-HSTiO2 should be attributed to the presence of abundant surface active sites of HSTiO2, remarkably extending electronic holes in Au doping. This study provides a promising photosynthetic material for hydrogen production.
In this paper, we report our attempts to raise the efficiency of liquid reduction method when using high specific surface area TiO2 (HSTiO2) by doping Au. Characterization of Au-HSTiO2 was conducted via XRD, UV-vis, SEM, and photocurrent intensity. The experimental results show that Au-HSTiO2 exhibits prominently higher photocatalytic hydrogen production than TiO2 and HSTiO2. Enhanced photosynthetic hydrogen production ability of Au-HSTiO2 should be attributed to the presence of abundant surface active sites of HSTiO2, remarkably extending electronic holes in Au doping. This study provides a promising photosynthetic material for hydrogen production.
2020, 39(8): 1444-1450
doi: 10.14102/j.cnki.0254–5861.2011–2635
Abstract:
Pharmaceutical cocrystal, as a new solid modification, has attracted more and more attention, which can improve the solubility and bioavailability of oral drugs. Ibuprofen is classified as a biopharmaceutical classification system class II drug with high permeability but low solubility. The main task of this paper was to improve the physicochemical properties of IBU by designing and systhesizing cocrystals. Ibuprofen-isonicotinamide was prepared by solvent evaporation method combined with ultrasound technology. Solid state characterization by powder X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and fourier transform infrared spectroscopy showed that a new crystalline phase was successfully formed. Single-crystal X-ray diffraction results showed that hydrogen bonds were formed between ibuprofen and isonicotinamide with the molar ratio of 1:1. The aqueous solubility results showed that the formation of cocrystal increased the solubility twice while did not affect the stability of ibuprofen in simulated gastric fluid. In addition, melting point and bond length theory were used to analyze the product and judged that the product is cocrystal rather than salt.
Pharmaceutical cocrystal, as a new solid modification, has attracted more and more attention, which can improve the solubility and bioavailability of oral drugs. Ibuprofen is classified as a biopharmaceutical classification system class II drug with high permeability but low solubility. The main task of this paper was to improve the physicochemical properties of IBU by designing and systhesizing cocrystals. Ibuprofen-isonicotinamide was prepared by solvent evaporation method combined with ultrasound technology. Solid state characterization by powder X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and fourier transform infrared spectroscopy showed that a new crystalline phase was successfully formed. Single-crystal X-ray diffraction results showed that hydrogen bonds were formed between ibuprofen and isonicotinamide with the molar ratio of 1:1. The aqueous solubility results showed that the formation of cocrystal increased the solubility twice while did not affect the stability of ibuprofen in simulated gastric fluid. In addition, melting point and bond length theory were used to analyze the product and judged that the product is cocrystal rather than salt.
2020, 39(8): 1451-1457
doi: 10.14102/j.cnki.0254–5861.2011–2711
Abstract:
Two new coordination complexes [Cd(L)2(1,2,3-HBTC)]·3H2O (1) and {[Zn(L)(1,2-BDC)]·H2O}n (2) were synthesized under hydrothermal conditions (1,2,3-H3BTC = 1,2,3-tricarboxybenzene, 1,2-H2BDC = 1,2-dicarboxybenzene and L = 2,2'-H2biimidazole). 1 crystallizes in monoclinic, space group P21/c with a = 12.256(5), b = 11.620(5), c = 17.479(5) Å, β = 95.548(5)o, V = 2477.6(16) Å3, Z = 4, C21H22N8O9Cd, Mr = 642.86, Dc = 1.724 g/cm3, F(000) = 1296, μ(MoKa) = 0.950 mm–1, R = 0.0546 and wR = 0.1724. 2 belongs to the monoclinic system, space group P21/c with a = 7.408(4), b = 20.743(10), c = 10.194(5) Å, β = 95.648(6)o, V = 1477.3(12) Å3, Z = 4, C14H12N4O5Zn, Mr = 381.65, Dc = 1.716 g/cm3, F(000) = 776, μ(MoKa) = 1.698 mm–1, R = 0.0574 and wR = 0.1632. The central Cd(II) ion in 1 is coordinated with five atoms, forming a slightly distorted square-pyramidal geometry. The central Zn(II) ion in 2 is four-coordinated by two nitrogen atoms from one L ligand and two oxygen atoms from two different 1,2-BDC anions. In addition, luminescent property of 1 has been investigated, and natural bond orbital (NBO) analysis of 2 has been calculated by the B3LYP/LANL2DZ method.
Two new coordination complexes [Cd(L)2(1,2,3-HBTC)]·3H2O (1) and {[Zn(L)(1,2-BDC)]·H2O}n (2) were synthesized under hydrothermal conditions (1,2,3-H3BTC = 1,2,3-tricarboxybenzene, 1,2-H2BDC = 1,2-dicarboxybenzene and L = 2,2'-H2biimidazole). 1 crystallizes in monoclinic, space group P21/c with a = 12.256(5), b = 11.620(5), c = 17.479(5) Å, β = 95.548(5)o, V = 2477.6(16) Å3, Z = 4, C21H22N8O9Cd, Mr = 642.86, Dc = 1.724 g/cm3, F(000) = 1296, μ(MoKa) = 0.950 mm–1, R = 0.0546 and wR = 0.1724. 2 belongs to the monoclinic system, space group P21/c with a = 7.408(4), b = 20.743(10), c = 10.194(5) Å, β = 95.648(6)o, V = 1477.3(12) Å3, Z = 4, C14H12N4O5Zn, Mr = 381.65, Dc = 1.716 g/cm3, F(000) = 776, μ(MoKa) = 1.698 mm–1, R = 0.0574 and wR = 0.1632. The central Cd(II) ion in 1 is coordinated with five atoms, forming a slightly distorted square-pyramidal geometry. The central Zn(II) ion in 2 is four-coordinated by two nitrogen atoms from one L ligand and two oxygen atoms from two different 1,2-BDC anions. In addition, luminescent property of 1 has been investigated, and natural bond orbital (NBO) analysis of 2 has been calculated by the B3LYP/LANL2DZ method.
2020, 39(8): 1458-1464
doi: 10.14102/j.cnki.0254–5861.2011–2627
Abstract:
A three-dimensional (3D) zinc metal-organic framework (MOF), Zn4(µ4-O)(bcd)3 (complex 1) has been synthesized by using 1-[bis(4-carboxylphenyl)methyl]-1, 3-diazole (H2bcd) and Zn(NO3)2·6H2O under hydrothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 crystallizes in trigonal system, space group R\begin{document}$ \stackrel{-}{3} $\end{document}
A three-dimensional (3D) zinc metal-organic framework (MOF), Zn4(µ4-O)(bcd)3 (complex 1) has been synthesized by using 1-[bis(4-carboxylphenyl)methyl]-1, 3-diazole (H2bcd) and Zn(NO3)2·6H2O under hydrothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 crystallizes in trigonal system, space group R
2020, 39(8): 1465-1474
doi: 10.14102/j.cnki.0254–5861.2011–2603
Abstract:
Two new heterobimetallic coordination polymers {[Co(NiL)(H2O)3]·4H2O}n (1) and {[Cu(NiL)(H2O)3]·4H2O}n (2) were synthesized based on metalloligand under the same self-assembly conditions. X-ray diffraction analyses reveal that the two compounds involve close-packed zigzag chains, which expand into various three-dimensional supramolecular frameworks through the second interactions such as hydrogen bonds and π∙∙∙π stacking interactions. In these two compounds, NiL as a bridging ligand chelates the metal ion nodes via two oxamido carbonyls and carboxylate oxygen atom. The central Co(II) and Cu(II) ions in 1 and 2 both exhibit distorted octahedral coordination geometry. They are bridged by macrocyclic oxamido metalloligands fusing the zigzag chains with a ''head-to-tail'' arrangement. The Ni(II) ion in metalloligand is coordinated by four nitrogen atoms with the [NiN4] chromophore exhibiting distorted planarity. The two investigated compounds were further characterized by thermogravimetric analysis and FT-IR spectroscopy. The fluorescent properties of 1 and 2 in the solid state were also investigated.
Two new heterobimetallic coordination polymers {[Co(NiL)(H2O)3]·4H2O}n (1) and {[Cu(NiL)(H2O)3]·4H2O}n (2) were synthesized based on metalloligand under the same self-assembly conditions. X-ray diffraction analyses reveal that the two compounds involve close-packed zigzag chains, which expand into various three-dimensional supramolecular frameworks through the second interactions such as hydrogen bonds and π∙∙∙π stacking interactions. In these two compounds, NiL as a bridging ligand chelates the metal ion nodes via two oxamido carbonyls and carboxylate oxygen atom. The central Co(II) and Cu(II) ions in 1 and 2 both exhibit distorted octahedral coordination geometry. They are bridged by macrocyclic oxamido metalloligands fusing the zigzag chains with a ''head-to-tail'' arrangement. The Ni(II) ion in metalloligand is coordinated by four nitrogen atoms with the [NiN4] chromophore exhibiting distorted planarity. The two investigated compounds were further characterized by thermogravimetric analysis and FT-IR spectroscopy. The fluorescent properties of 1 and 2 in the solid state were also investigated.
2020, 39(8): 1475-1482
doi: 10.14102/j.cnki.0254–5861.2011–2605
Abstract:
A new Cu(II) coordination polymer, {[Cu3(oba)2(μ3-OH)2(H2O)2]⋅6H2O}n (H2oba = 4, 4΄-oxydibenzoic acid), was synthesized by the solvothermal route and characterized by IR, TGA and XRD. The complex crystallizes in the monoclinic system, space group P21/c with a = 5.957(6), b = 29.746(3), c = 9.351(7) Å, β = 125.709(4)º, V = 1345.4(2) Å3, Z = 2, C28H36Cu3O20, Mr= 883.09, Dc = 1.913 g/cm3, F(000) = 782, μ = 2.427 mm-1, R = 0.0780 and wR= 0.1688 for 3120 observed reflections with I > 2σ(I). The complex forms a 3D framework based on rare infinite rod-shaped secondary building units (SBUs), and C–H···π interactions play an important role in stabilizing the 3D supramolecular architecture. It shows excellent catalytic activities for the degradation of safranin O (SO) and methylene blue (MB) dyes in aqueous solution under UV light irradiation. Furthermore, the apparent rate constants have also been investigated.
A new Cu(II) coordination polymer, {[Cu3(oba)2(μ3-OH)2(H2O)2]⋅6H2O}n (H2oba = 4, 4΄-oxydibenzoic acid), was synthesized by the solvothermal route and characterized by IR, TGA and XRD. The complex crystallizes in the monoclinic system, space group P21/c with a = 5.957(6), b = 29.746(3), c = 9.351(7) Å, β = 125.709(4)º, V = 1345.4(2) Å3, Z = 2, C28H36Cu3O20, Mr= 883.09, Dc = 1.913 g/cm3, F(000) = 782, μ = 2.427 mm-1, R = 0.0780 and wR= 0.1688 for 3120 observed reflections with I > 2σ(I). The complex forms a 3D framework based on rare infinite rod-shaped secondary building units (SBUs), and C–H···π interactions play an important role in stabilizing the 3D supramolecular architecture. It shows excellent catalytic activities for the degradation of safranin O (SO) and methylene blue (MB) dyes in aqueous solution under UV light irradiation. Furthermore, the apparent rate constants have also been investigated.
2020, 39(8): 1483-1488
doi: 10.14102/j.cnki.0254–5861.2011–2613
Abstract:
Two Cd(II) and Co(II)-based complexes formulated as [Cd(bimh)(L)]·2H2O (1) and [Co(bimh)-(L)]·2H2O (2) (bimh = 1, 6-bis(imidazole-1-yl)hexane, H2L = 4, 4΄-(methylenebis(oxy))dibenzoic acid) have been successfully prepared under hydrothermal conditions. Single-crystal X-ray diffraction analysis indicates that the two complexes are isostructural and crystallize in Pbca space group. The whole three-dimensional (3D) architecture is based on three-fold interpenetrated layers containing double helical chains. In addition, the IR, TG and photoluminescence properties were also investigated.
Two Cd(II) and Co(II)-based complexes formulated as [Cd(bimh)(L)]·2H2O (1) and [Co(bimh)-(L)]·2H2O (2) (bimh = 1, 6-bis(imidazole-1-yl)hexane, H2L = 4, 4΄-(methylenebis(oxy))dibenzoic acid) have been successfully prepared under hydrothermal conditions. Single-crystal X-ray diffraction analysis indicates that the two complexes are isostructural and crystallize in Pbca space group. The whole three-dimensional (3D) architecture is based on three-fold interpenetrated layers containing double helical chains. In addition, the IR, TG and photoluminescence properties were also investigated.
2020, 39(8): 1489-1495
doi: 10.14102/j.cnki.0254–5861.2011–2620
Abstract:
Metal-organic frameworks are a sort of rapid development crystal solids, which have greatly attracted a large amount of attention in recent decades. The construction of 3D [Ni(bcp)(bpp)]n (namely complex 1) displays a rare [3+3+3] nine-fold interpenetrated diamond topology, which can be successfully synthesized by a mixed strategy of 1, 3-bis(4-carboxyphenoxy) propane (H2bcp) and 1, 4-bis(4-pyridylmethyl) piperazine (bpp). The interpenetrated network may be ascribed to these flexible bridging linkers to facilitate the penetration degree. In addition, the resultant sample was adequately characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal gravimetric analysis. Furthermore, the as-synthesized sample can be used as catalysis for chemical fixation of CO2 and epoxide to carbonate.
Metal-organic frameworks are a sort of rapid development crystal solids, which have greatly attracted a large amount of attention in recent decades. The construction of 3D [Ni(bcp)(bpp)]n (namely complex 1) displays a rare [3+3+3] nine-fold interpenetrated diamond topology, which can be successfully synthesized by a mixed strategy of 1, 3-bis(4-carboxyphenoxy) propane (H2bcp) and 1, 4-bis(4-pyridylmethyl) piperazine (bpp). The interpenetrated network may be ascribed to these flexible bridging linkers to facilitate the penetration degree. In addition, the resultant sample was adequately characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal gravimetric analysis. Furthermore, the as-synthesized sample can be used as catalysis for chemical fixation of CO2 and epoxide to carbonate.
2020, 39(8): 1496-1502
doi: 10.14102/j.cnki.0254–5861.2011–2623
Abstract:
A water-stable porous anionic metal-organic framework (MOF), [(CH3)2NH2][In(TCPP)4/3]n· (2DMF)n(3H2O)n (1, TCPP = 1, 1, 2, 2-tetra(4-carboxylbiphenyl)ethylene), was synthesized. Here, compound 1 showed extremely high sensitivity and selectivity to current general-purpose pesticide 2, 6-dichloro-4-nitroaniline (DCN) in aqueous solution. The fluorescence intensity of compound 1 could be decreased as much as 80% by 6 μL DCN, and it was almost completely quenched only with 20 μL DCN. The results indicate that compound 1 can act as a fluorescent probe for DCN.
A water-stable porous anionic metal-organic framework (MOF), [(CH3)2NH2][In(TCPP)4/3]n· (2DMF)n(3H2O)n (1, TCPP = 1, 1, 2, 2-tetra(4-carboxylbiphenyl)ethylene), was synthesized. Here, compound 1 showed extremely high sensitivity and selectivity to current general-purpose pesticide 2, 6-dichloro-4-nitroaniline (DCN) in aqueous solution. The fluorescence intensity of compound 1 could be decreased as much as 80% by 6 μL DCN, and it was almost completely quenched only with 20 μL DCN. The results indicate that compound 1 can act as a fluorescent probe for DCN.
2020, 39(8): 1503-1508
doi: 10.14102/j.cnki.0254–5861.2011–2625
Abstract:
Under solvothermal conditions, two ribbon-shaped chalcogenidometalate coordination compounds, (butyl-Sn)4S8M2(TEPA)2 (M = Mn (1), Ni (2), TEPA = tetraethylenepentamine), have been synthesized and characterized by elemental analysis, energy dispersive X-ray, infrared/ultraviolet-visible spectroscopy, thermo-gravimetric analysis, single-crystal and powder X-ray diffraction. Complexes 1 and 2 crystallize in the triclinic space group P\begin{document}$ \overline 1 $\end{document}
Under solvothermal conditions, two ribbon-shaped chalcogenidometalate coordination compounds, (butyl-Sn)4S8M2(TEPA)2 (M = Mn (1), Ni (2), TEPA = tetraethylenepentamine), have been synthesized and characterized by elemental analysis, energy dispersive X-ray, infrared/ultraviolet-visible spectroscopy, thermo-gravimetric analysis, single-crystal and powder X-ray diffraction. Complexes 1 and 2 crystallize in the triclinic space group P
2020, 39(8): 1509-1514
doi: 10.14102/j.cnki.0254–5861.2011–2632
Abstract:
A new coordination polymer, [Co2(L)2(H2O)2]n·H2O (1, H2L = 5-(1H-1, 2, 4-triazol-1-yl)-1, 3-benzenedicarboxylic acid), was constructed by hydrothermal condition reaction of Co(NO3)2·6H2O and H2L at the pH value of 5.6. The as-prepared complex 1 was characterized by elemental analysis, IR and single-crystal X-ray diffraction. Furthermore, a green hand grinding technique has been implemented to reduce the particle size of complex 1 to generate nanoscale 1 (denoted as nano 1 hereafter) with spherical morphology. Furthermore, the treatment of the compound on anxiety and insomnia was evaluated. Firstly, the ELISA was used to detect the content of serotonin, gamma-aminobutyric acid in the brain. Besides, the Rat sleep phase detection was determined by pentobarbital synergistic sleep experiment.
A new coordination polymer, [Co2(L)2(H2O)2]n·H2O (1, H2L = 5-(1H-1, 2, 4-triazol-1-yl)-1, 3-benzenedicarboxylic acid), was constructed by hydrothermal condition reaction of Co(NO3)2·6H2O and H2L at the pH value of 5.6. The as-prepared complex 1 was characterized by elemental analysis, IR and single-crystal X-ray diffraction. Furthermore, a green hand grinding technique has been implemented to reduce the particle size of complex 1 to generate nanoscale 1 (denoted as nano 1 hereafter) with spherical morphology. Furthermore, the treatment of the compound on anxiety and insomnia was evaluated. Firstly, the ELISA was used to detect the content of serotonin, gamma-aminobutyric acid in the brain. Besides, the Rat sleep phase detection was determined by pentobarbital synergistic sleep experiment.
2020, 39(8): 1515-1521
doi: 10.14102/j.cnki.0254–5861.2011–2624
Abstract:
Rare earth phosphates have been used extensively in luminescent phosphors. Hexagonal Ce1-xGdxPO4 with crystal field manipulation was successfully synthesized using a hydrothermal method. The photoluminescence emission intensity of hexagonal CePO4 was obviously enhanced by the crystal structure manipulation with gadolinium ions codoping. Compared to pure CePO4, the intensity photoluminescence was enhanced about 15 folds with x = 0.05. The effect of gadolinium doping was systematically investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and photoluminescence spectroscopy. Crystal field asymmetry can be effectively tuned by different amount of Gd3+ codoping, and the crystal field asymmetry is conductive to electron population of high energy level of Ce3+ ions. This material has potential applications in optics, electronics fields, and so on. Meanwhile, the method can be extended to another kind of high performance photoluminescence materials preparation.
Rare earth phosphates have been used extensively in luminescent phosphors. Hexagonal Ce1-xGdxPO4 with crystal field manipulation was successfully synthesized using a hydrothermal method. The photoluminescence emission intensity of hexagonal CePO4 was obviously enhanced by the crystal structure manipulation with gadolinium ions codoping. Compared to pure CePO4, the intensity photoluminescence was enhanced about 15 folds with x = 0.05. The effect of gadolinium doping was systematically investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and photoluminescence spectroscopy. Crystal field asymmetry can be effectively tuned by different amount of Gd3+ codoping, and the crystal field asymmetry is conductive to electron population of high energy level of Ce3+ ions. This material has potential applications in optics, electronics fields, and so on. Meanwhile, the method can be extended to another kind of high performance photoluminescence materials preparation.
2020, 39(8): 1522-1530
doi: 10.14102/j.cnki.0254–5861.2011–2644
Abstract:
Cu2O/Cu nanoparticles (NPs) in the nanoporous carbon matrix (designated as Cu2O/Cu@NPC) has been synthesized by in-situ calcination of a cupper-based metal-organic framework (Cu-MOF), and its morphology and composition were characterized by PXRD, SEM and Raman. Furthermore, elemental mapping and XPS analysis not only show Cu NPs is generated along with nitrogen (N)-doped carbon, but also indicate Cu2O NPs locates in the external layer of Cu@NPC. In addition, the adsorption of dye studies implies that Cu2O/Cu@NPC exhibits obvious interaction with Rhodamine B (Rh B) due to the feature of porous and N-doped structure. Cu2O/Cu@NPC has highly electrocatalytic performance for glucose and mercury(II) with wide detection range and good stability, which can be used as a novel multifunctional sensor for glucose and mercury(II).
Cu2O/Cu nanoparticles (NPs) in the nanoporous carbon matrix (designated as Cu2O/Cu@NPC) has been synthesized by in-situ calcination of a cupper-based metal-organic framework (Cu-MOF), and its morphology and composition were characterized by PXRD, SEM and Raman. Furthermore, elemental mapping and XPS analysis not only show Cu NPs is generated along with nitrogen (N)-doped carbon, but also indicate Cu2O NPs locates in the external layer of Cu@NPC. In addition, the adsorption of dye studies implies that Cu2O/Cu@NPC exhibits obvious interaction with Rhodamine B (Rh B) due to the feature of porous and N-doped structure. Cu2O/Cu@NPC has highly electrocatalytic performance for glucose and mercury(II) with wide detection range and good stability, which can be used as a novel multifunctional sensor for glucose and mercury(II).
2020, 39(8): 1531-1538
doi: 10.14102/j.cnki.0254–5861.2011–2671
Abstract:
The title compound phenyl(6-phenyl-3-p-tolyl-6, 7-dihydro-5H-[1,2,4]triazolo[3, 4-b][1,3,4]thia-diazin-7-yl)methanone (PTM), designed using 4-amino-3-p-tolyl-1H-1, 2, 4-triazole-5(4H)-thione as the starting material, was successfully synthesized via a two-step synthesis route and finally characterized by NMR, FT-IR, single-crystal X-ray diffraction and mass spectrometry techniques. The crystal structure of trans-PTM was obtained from X-ray diffraction: C24H20N4OS, Mr = 412.52, monoclinic system, space group P21/c, a = 16.650(3), b = 13.876(3), c = 8.812(2) Å, β = 100.340(3)°, V = 2002.8(7) Å3, F(000) = 865, Z = 4, Dc = 1.3680 g/cm3, λ = 0.71073 Å, μ = 0.186 mm‑1 and the final R = 0.0786 for 3514 unique reflections with 2044 observed ones (I > 2σ(I)). The biological activities of antimicrobial and regulation of plant growth of PTM were investigated. The results indicated that PTM showed weak antimicrobial activity on Bacillus pumilus, while promoted the growth of radish and inhibited that of wheat in a dose-dependent manner. Therefore, PTM may be developed as a potential drug to promote the growth of dicotyledonous plants or as an herbicide to inhibit that of monocotyledonous plants in the future.
The title compound phenyl(6-phenyl-3-p-tolyl-6, 7-dihydro-5H-[1,2,4]triazolo[3, 4-b][1,3,4]thia-diazin-7-yl)methanone (PTM), designed using 4-amino-3-p-tolyl-1H-1, 2, 4-triazole-5(4H)-thione as the starting material, was successfully synthesized via a two-step synthesis route and finally characterized by NMR, FT-IR, single-crystal X-ray diffraction and mass spectrometry techniques. The crystal structure of trans-PTM was obtained from X-ray diffraction: C24H20N4OS, Mr = 412.52, monoclinic system, space group P21/c, a = 16.650(3), b = 13.876(3), c = 8.812(2) Å, β = 100.340(3)°, V = 2002.8(7) Å3, F(000) = 865, Z = 4, Dc = 1.3680 g/cm3, λ = 0.71073 Å, μ = 0.186 mm‑1 and the final R = 0.0786 for 3514 unique reflections with 2044 observed ones (I > 2σ(I)). The biological activities of antimicrobial and regulation of plant growth of PTM were investigated. The results indicated that PTM showed weak antimicrobial activity on Bacillus pumilus, while promoted the growth of radish and inhibited that of wheat in a dose-dependent manner. Therefore, PTM may be developed as a potential drug to promote the growth of dicotyledonous plants or as an herbicide to inhibit that of monocotyledonous plants in the future.
2020, 39(8): 1539-1545
doi: 10.14102/j.cnki.0254–5861.2011–2640
Abstract:
The title compounds (7a~7g) were synthesized from dehydroabietic acid and characterized by spectroscopic methods including HR-MS, 1H- and 13C-NMR. The crystal structure of compound 7g determined by single-crystal X-ray diffractio is of monoclinic system, space group P21 with a = 12.282(3), b = 9.940(2), c = 22.656(5) Å, β = 103.06(3)°, Z = 2, V = 2694.4(10) Å3, Mr = 1182.95, Dc = 1.458 Mg/m3, S = 1.000, μ = 1.649 mm-1, F(000) = 1216, the final R = 0.0791 and wR = 0.1853 for 4098 observed reflections (I > 2σ(I)). The preliminary antibacterial assay showed that compound 7g exhibits significant inhibitory against Bacillus subtilis, Staphylococcus aureus and Methicillin-resistant S. aureus (MRSA) with MIC values of 1.9~7.8 μg/mL.
The title compounds (7a~7g) were synthesized from dehydroabietic acid and characterized by spectroscopic methods including HR-MS, 1H- and 13C-NMR. The crystal structure of compound 7g determined by single-crystal X-ray diffractio is of monoclinic system, space group P21 with a = 12.282(3), b = 9.940(2), c = 22.656(5) Å, β = 103.06(3)°, Z = 2, V = 2694.4(10) Å3, Mr = 1182.95, Dc = 1.458 Mg/m3, S = 1.000, μ = 1.649 mm-1, F(000) = 1216, the final R = 0.0791 and wR = 0.1853 for 4098 observed reflections (I > 2σ(I)). The preliminary antibacterial assay showed that compound 7g exhibits significant inhibitory against Bacillus subtilis, Staphylococcus aureus and Methicillin-resistant S. aureus (MRSA) with MIC values of 1.9~7.8 μg/mL.
2020, 39(8): 1546-1552
doi: 10.14102/j.cnki.0254–5861.2011–2688
Abstract:
The title compound (E)-2-(2-(4, 8, 8-trimethyldecahydro-1, 4-methanoazulen-9-ylidene)ethyl)benzo[d]isothiazol-3(2H)-one (Ic) was synthesized from longifolene and 1, 2-benzoisothiazolinone (short as BIT) through Prins, halogenation and nitro-alkylation reaction and structurally identified by means of HRMS, IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction. The crystal of compound Ic is of bi-molecular structure and belongs to orthorhombic system, P212121 space group with a = 7.5715(7), b = 16.8824(9), c = 31.1926(14) Å, V = 3987.2(5) Å3, Mr = 367.53, Dc = 1.225 mg/m3, Z = 8, μ = 0.174 mm–1 and F(000) = 1584. A total of 17045 reflections were collected, of which 7306 were unique (Rint = 0.0566). The structure was refined to R = 0.0967 and wR = 0.1998 for 7306 observed reflections with I > 2σ(I). 1D chain along the a-axis is formed by two types of π-π interactions between benzene rings from adjacent molecules. Especially, compound Ic shows improved solubility in nonpolar organic solvents and higher antimicrobial activity than longifolene and BIT against bacteria and fungi. The minimum inhibition concentration (MIC) of Ic against two Gram-positive bacteria (S. aureus and B. subtili), two Gram-negative bacteria (E. coli and K. pneumoniae) and three fungi (C. albicans, C. tropicalis and A. niger) are 0.242, 0.242, 15.6, 15.6, 1.95, 1.95 and 1.95 µg/mL, respectively.
The title compound (E)-2-(2-(4, 8, 8-trimethyldecahydro-1, 4-methanoazulen-9-ylidene)ethyl)benzo[d]isothiazol-3(2H)-one (Ic) was synthesized from longifolene and 1, 2-benzoisothiazolinone (short as BIT) through Prins, halogenation and nitro-alkylation reaction and structurally identified by means of HRMS, IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction. The crystal of compound Ic is of bi-molecular structure and belongs to orthorhombic system, P212121 space group with a = 7.5715(7), b = 16.8824(9), c = 31.1926(14) Å, V = 3987.2(5) Å3, Mr = 367.53, Dc = 1.225 mg/m3, Z = 8, μ = 0.174 mm–1 and F(000) = 1584. A total of 17045 reflections were collected, of which 7306 were unique (Rint = 0.0566). The structure was refined to R = 0.0967 and wR = 0.1998 for 7306 observed reflections with I > 2σ(I). 1D chain along the a-axis is formed by two types of π-π interactions between benzene rings from adjacent molecules. Especially, compound Ic shows improved solubility in nonpolar organic solvents and higher antimicrobial activity than longifolene and BIT against bacteria and fungi. The minimum inhibition concentration (MIC) of Ic against two Gram-positive bacteria (S. aureus and B. subtili), two Gram-negative bacteria (E. coli and K. pneumoniae) and three fungi (C. albicans, C. tropicalis and A. niger) are 0.242, 0.242, 15.6, 15.6, 1.95, 1.95 and 1.95 µg/mL, respectively.
