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2022 Volume 41 Issue 2
2022, 41(2): 220200
doi: 10.14102/j.cnki.0254-5861.2011-3268
Abstract:
The chemokine receptor CCR5 is a main and necessary co-receptor for which HIV can recognize and enter the cells, and has been identified as a potential new target for the design of new anti-HIV therapeutic drugs. Highly active CCR5 inhibitors can prevent HIV-1 from entering target cells and block the process of infection. In this study, HQSAR and Topomer CoMFA methods were used to establish QSAR models for 75 1-(3, 3-diphenylpropyl)-piperidinyl and urea derivatives, and cross-validation and non-cross-validation were performed on the generated models. Two models with good statistical parameters and reliable prediction capabilities are obtained: (Topomer CoMFA: q2 = 0.687, r2 = 0.868, rpred2 = 0.623; HQSAR: q2 = 0.781, r2 = 0.921, rpred2 = 0.636). Contour maps and color code maps provide a lot of useful information for determining structural requirements that affect activity. Topomer search technology was used for virtual screening and molecular design. Surfex-dock method and ADMET technology were used to conduct molecular docking, oral bioavailability and toxicity prediction of the designed drug molecules. Results showed that A/ASN425, A/GLY198 and A/TRP427 may be the potential active residues of CCR5 inhibitors evaluated in this study, with 40 newly designed 1-(3, 3-diphenylpropyl)-piperidinyl and urea derivatives which have the main ADMET properties and can be used as a reliable anti-HIV inhibitor. These results provide a certain theoretical basis for the experimental verification of new compounds in the future.
The chemokine receptor CCR5 is a main and necessary co-receptor for which HIV can recognize and enter the cells, and has been identified as a potential new target for the design of new anti-HIV therapeutic drugs. Highly active CCR5 inhibitors can prevent HIV-1 from entering target cells and block the process of infection. In this study, HQSAR and Topomer CoMFA methods were used to establish QSAR models for 75 1-(3, 3-diphenylpropyl)-piperidinyl and urea derivatives, and cross-validation and non-cross-validation were performed on the generated models. Two models with good statistical parameters and reliable prediction capabilities are obtained: (Topomer CoMFA: q2 = 0.687, r2 = 0.868, rpred2 = 0.623; HQSAR: q2 = 0.781, r2 = 0.921, rpred2 = 0.636). Contour maps and color code maps provide a lot of useful information for determining structural requirements that affect activity. Topomer search technology was used for virtual screening and molecular design. Surfex-dock method and ADMET technology were used to conduct molecular docking, oral bioavailability and toxicity prediction of the designed drug molecules. Results showed that A/ASN425, A/GLY198 and A/TRP427 may be the potential active residues of CCR5 inhibitors evaluated in this study, with 40 newly designed 1-(3, 3-diphenylpropyl)-piperidinyl and urea derivatives which have the main ADMET properties and can be used as a reliable anti-HIV inhibitor. These results provide a certain theoretical basis for the experimental verification of new compounds in the future.
2022, 41(2): 220201
doi: 10.14102/j.cnki.0254-5861.2011-3234
Abstract:
Two new 3-D Cd(II) coordination polymers with p-phthalic acid (p-BDC) and 4, 4΄-dipyridylamine (4, 4΄-dpa), namely [Cd2(p-BDC)2(4, 4΄-dpa)2]n 1 and {[Cd(p-BDC)(4, 4΄-dpa) (H2O)]·4H2O}n 2 were successfully synthesized under hydrothermal conditions at 120 and 140 ℃. They were characterized by single-crystal X-ray diffraction, IR, PXRD and TGA. It was further characterized by Hirshfeld surface (HS) analysis for complex 2. The luminescent properties of the complexes have also been investigated.
Two new 3-D Cd(II) coordination polymers with p-phthalic acid (p-BDC) and 4, 4΄-dipyridylamine (4, 4΄-dpa), namely [Cd2(p-BDC)2(4, 4΄-dpa)2]n 1 and {[Cd(p-BDC)(4, 4΄-dpa) (H2O)]·4H2O}n 2 were successfully synthesized under hydrothermal conditions at 120 and 140 ℃. They were characterized by single-crystal X-ray diffraction, IR, PXRD and TGA. It was further characterized by Hirshfeld surface (HS) analysis for complex 2. The luminescent properties of the complexes have also been investigated.
2022, 41(2): 220202
doi: 10.14102/j.cnki.0254-5861.2011-3243
Abstract:
A new lanthanide metal-organic framework (MOF) [Eu(BTB)(phen)(DMF)]žDMF (1, DMF = N, N-dimethylformamide) was synthesized using H3BTB (1, 3, 5-tri(4-carboxyphenyl)benzene) and phen (1, 10-phenanthroline) under solvothermal conditions. The structure of the prepared MOF was characterized by single-crystal X-ray diffraction analyses, elemental analysis, fluorescence spectrum, FT-IR spectroscopy, powder X-ray diffraction and thermogravimetric analyses. The structure of 1 can be viewed as a 3-D supramolecular network, which is formed by the stacking of 2D layers through π-π interaction. The luminescence explorations revealed that 1 possesses favorable selectivity and sensitivity for testing Fe3+. Additionally, color tuning was achieved by varying Eu3+: Tb3+ ratios in the reaction mixtures.
A new lanthanide metal-organic framework (MOF) [Eu(BTB)(phen)(DMF)]žDMF (1, DMF = N, N-dimethylformamide) was synthesized using H3BTB (1, 3, 5-tri(4-carboxyphenyl)benzene) and phen (1, 10-phenanthroline) under solvothermal conditions. The structure of the prepared MOF was characterized by single-crystal X-ray diffraction analyses, elemental analysis, fluorescence spectrum, FT-IR spectroscopy, powder X-ray diffraction and thermogravimetric analyses. The structure of 1 can be viewed as a 3-D supramolecular network, which is formed by the stacking of 2D layers through π-π interaction. The luminescence explorations revealed that 1 possesses favorable selectivity and sensitivity for testing Fe3+. Additionally, color tuning was achieved by varying Eu3+: Tb3+ ratios in the reaction mixtures.
2022, 41(2): 220203
doi: 10.14102/j.cnki.0254-5861.2011-3250
Abstract:
Two cadmium(II) coordination polymers, namely [Cd(μ-dda)(H2biim)]n (1) and [Cd(μ4-dda)(py)]n (2) have been constructed hydrothermally using H2dda (H2dda = 4, 4΄-dihydroxybiphenyl-3, 3΄-dicarboxylic acid), H2biim (H2biim = 2, 2΄-biimidazole), py (py = pyridine), and cadmium chloride at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that both compounds crystallize in the monoclinic system, space group C2/c. Compound 1 discloses a 1D chain structure. Compound 2 features a 3D framework. The luminescent properties of compounds 1 and 2 were evaluated. Besides, the catalytic activities in the Knoevenagel condensation reaction of two compounds were investigated. Compound 1 exhibits an excellent catalytic activity in the Knoevenagel condensation reaction at room temperature.
Two cadmium(II) coordination polymers, namely [Cd(μ-dda)(H2biim)]n (1) and [Cd(μ4-dda)(py)]n (2) have been constructed hydrothermally using H2dda (H2dda = 4, 4΄-dihydroxybiphenyl-3, 3΄-dicarboxylic acid), H2biim (H2biim = 2, 2΄-biimidazole), py (py = pyridine), and cadmium chloride at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that both compounds crystallize in the monoclinic system, space group C2/c. Compound 1 discloses a 1D chain structure. Compound 2 features a 3D framework. The luminescent properties of compounds 1 and 2 were evaluated. Besides, the catalytic activities in the Knoevenagel condensation reaction of two compounds were investigated. Compound 1 exhibits an excellent catalytic activity in the Knoevenagel condensation reaction at room temperature.
2022, 41(2): 220204
doi: 10.14102/j.cnki.0254-5861.2011-3245
Abstract:
A viologen-bearing Zn(II) coordination polymer, [Zn(Bpybc)SO4]·H2O, has been successfully synthesized and structurally characterized. The title compound exhibits sunlight and UV-induced photochromism, thermoschromism, and amine-selective chemochromism.
A viologen-bearing Zn(II) coordination polymer, [Zn(Bpybc)SO4]·H2O, has been successfully synthesized and structurally characterized. The title compound exhibits sunlight and UV-induced photochromism, thermoschromism, and amine-selective chemochromism.
2022, 41(2): 220204
doi: 10.14102/j.cnki.0254-5861.2011-3264
Abstract:
Three zinc(II) metal-organic frameworks (xF-MAC-3) have been synthesized by using Zn(II) salts, 3, 5-dimethyl-1H-1, 2, 4-triazole (Hdmtrz) and different fluorination degree carboxylate ligands, which are analogic structures and can be described as (6, 6)-connected pcu-b net. We find that the fluorine atoms have structural regulation effect on xF-MAC-3, which can not only enlarge the torsion angle ? of carboxylate ligands but also elevate the space group of structures. Besides, the CO2-273 K uptake increased from 23.21 cm3·g-1 (MAC-3) to 36.13 cm3·g-1 (4F-MAC-3) and H2-77 K uptake increased from 24.33 cm3·g-1 (MAC-3) to 59.79 cm3·g-1 (4F-MAC-3), which means fluorination can enhance the gas adsorption uptake of xF-MAC-3 analogues. Furthermore, the results of fluorination in xF-MAC-3 analogues offer a potential way to study the ligand pre-functionalization effect on the structures and properties of MOFs analogues.
Three zinc(II) metal-organic frameworks (xF-MAC-3) have been synthesized by using Zn(II) salts, 3, 5-dimethyl-1H-1, 2, 4-triazole (Hdmtrz) and different fluorination degree carboxylate ligands, which are analogic structures and can be described as (6, 6)-connected pcu-b net. We find that the fluorine atoms have structural regulation effect on xF-MAC-3, which can not only enlarge the torsion angle ? of carboxylate ligands but also elevate the space group of structures. Besides, the CO2-273 K uptake increased from 23.21 cm3·g-1 (MAC-3) to 36.13 cm3·g-1 (4F-MAC-3) and H2-77 K uptake increased from 24.33 cm3·g-1 (MAC-3) to 59.79 cm3·g-1 (4F-MAC-3), which means fluorination can enhance the gas adsorption uptake of xF-MAC-3 analogues. Furthermore, the results of fluorination in xF-MAC-3 analogues offer a potential way to study the ligand pre-functionalization effect on the structures and properties of MOFs analogues.
2022, 41(2): 220205
doi: 10.14102/j.cnki.0254-5861.2011-3257
Abstract:
A new complex [Cu1.5(tfc)3(H2O)4]·3H2O (1, Htfc = 4-(trifluoro-methyl) nicotinic acid) has been synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, IR spectra and thermo-gravimetric analysis. 1 belongs to orthorhombic system, space group Pccn with a = 44.507(2), b = 10.7710(6), c = 11.7544(7) Å, V = 5634.9(6) Å3, Z = 1, Dc = 1.803 mg·cm-3, F(000) = 3068, μ = 1.266 mm-1, the final R = 0.0488 and wR = 0.1103 with I > 2σ(I). The Cu(II) ion is coordinated by two N and two O atoms from different Htfc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral geometry. The adjacent 0D units are linked into 2D structures through bridge connection coordination mode. In addition, the binding properties of the complex with CT-DNA were investigated by fluorescence and ultraviolet spectra. UV spectra indicate classical intercalation between the complex and CT-DNA. Moreover, the interactions between the ligand and the complex with CT-DNA were studied by EtBr fluorescence probe, which proved that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.76 and 1.15 for Htfc and complex 1, which means 1 has stronger interaction with CT-DNA than Htfc.
A new complex [Cu1.5(tfc)3(H2O)4]·3H2O (1, Htfc = 4-(trifluoro-methyl) nicotinic acid) has been synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, IR spectra and thermo-gravimetric analysis. 1 belongs to orthorhombic system, space group Pccn with a = 44.507(2), b = 10.7710(6), c = 11.7544(7) Å, V = 5634.9(6) Å3, Z = 1, Dc = 1.803 mg·cm-3, F(000) = 3068, μ = 1.266 mm-1, the final R = 0.0488 and wR = 0.1103 with I > 2σ(I). The Cu(II) ion is coordinated by two N and two O atoms from different Htfc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral geometry. The adjacent 0D units are linked into 2D structures through bridge connection coordination mode. In addition, the binding properties of the complex with CT-DNA were investigated by fluorescence and ultraviolet spectra. UV spectra indicate classical intercalation between the complex and CT-DNA. Moreover, the interactions between the ligand and the complex with CT-DNA were studied by EtBr fluorescence probe, which proved that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.76 and 1.15 for Htfc and complex 1, which means 1 has stronger interaction with CT-DNA than Htfc.
2022, 41(2): 220206
doi: 10.14102/j.cnki.0254-5861.2011-3266
Abstract:
Two new coordination compounds [Co(FDC)2(H2O)2]n (1) and [Cu(FDC)2(2, 2΄-bpy)]·DMF·H2O (2) (HFDC = 9-fluorenone-4-carboxylic acid, bpy = 2, 2΄-bipyridine, DMF = N, N-dimethylformamide) were prepared by the reactions of corresponding metal salts with a fluorene derivative ligand of HFDC. Both compounds were thoroughly analyzed by X-ray single-crystal diffraction, elemental analysis, IR spectra, PXRD and thermal analysis. Compound 1 features a 1D structure. Via two kinds of O‒H···O hydrogen bonds, such 1D chains self-assemble into a 3D supramolecular structure stabilized by the offset face-to-face π···π interactions. Compound 2 features a dinuclear structure which, via O‒H···O and C‒H···O hydrogen bonds, self-assembles into a 2D supramolecular layer strengthened by strong face-to-face π···π interactions. And variable-temperature magnetic susceptibilities of 1 and 2 indicate weak antiferromagnetic interactions between the Co(II) and Cu(II) metal ions.
Two new coordination compounds [Co(FDC)2(H2O)2]n (1) and [Cu(FDC)2(2, 2΄-bpy)]·DMF·H2O (2) (HFDC = 9-fluorenone-4-carboxylic acid, bpy = 2, 2΄-bipyridine, DMF = N, N-dimethylformamide) were prepared by the reactions of corresponding metal salts with a fluorene derivative ligand of HFDC. Both compounds were thoroughly analyzed by X-ray single-crystal diffraction, elemental analysis, IR spectra, PXRD and thermal analysis. Compound 1 features a 1D structure. Via two kinds of O‒H···O hydrogen bonds, such 1D chains self-assemble into a 3D supramolecular structure stabilized by the offset face-to-face π···π interactions. Compound 2 features a dinuclear structure which, via O‒H···O and C‒H···O hydrogen bonds, self-assembles into a 2D supramolecular layer strengthened by strong face-to-face π···π interactions. And variable-temperature magnetic susceptibilities of 1 and 2 indicate weak antiferromagnetic interactions between the Co(II) and Cu(II) metal ions.
2022, 41(2): 220214
doi: 10.14102/j.cnki.0254-5861.2011-3284
Abstract:
Composite borate-phosphate compounds have always attracted much attention for their structure diversity and interesting properties. In this work, a new borate-phosphate CsNa2Lu2(BO3)(PO4)2 (CNLBP) was found for the first time and its structure was characterized by single-crystal X-ray diffraction method. It crystallizes in orthorhombic system, space group Cmcm with a = 6.8750(5), b = 14.6919(1), c = 10.5581(7) Å, V = 1066.44(1) Å3, Z = 4, Mr = 777.58, Dc = 4.843 g/cm3, F(000) = 1368, μ(MoKα) = 22.20 mm-1, R(F2 > 2σ(F2)) = 0.0173 and wR(F2) = 0.0367. The structure of CNLBP features a chain framework of [Lu2(BO3)(PO4)2]∞ that delimits 1D tunnels filled by Na+ and Cs+ ions. Phosphors CNLBP: xTb (x = 0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0) were prepared, and it can emit bright green light under near-UV excitation due to the 5D4→7Fj (j = 6, 5, 4, 3) transition of Tb3+. Due to the large separation of Lu3+ ions in CNLBP structure lattice, the optimal concentration of Tb3+ is 80%, and concentration quenching occurs only for the full Tb3+ concentration.
Composite borate-phosphate compounds have always attracted much attention for their structure diversity and interesting properties. In this work, a new borate-phosphate CsNa2Lu2(BO3)(PO4)2 (CNLBP) was found for the first time and its structure was characterized by single-crystal X-ray diffraction method. It crystallizes in orthorhombic system, space group Cmcm with a = 6.8750(5), b = 14.6919(1), c = 10.5581(7) Å, V = 1066.44(1) Å3, Z = 4, Mr = 777.58, Dc = 4.843 g/cm3, F(000) = 1368, μ(MoKα) = 22.20 mm-1, R(F2 > 2σ(F2)) = 0.0173 and wR(F2) = 0.0367. The structure of CNLBP features a chain framework of [Lu2(BO3)(PO4)2]∞ that delimits 1D tunnels filled by Na+ and Cs+ ions. Phosphors CNLBP: xTb (x = 0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0) were prepared, and it can emit bright green light under near-UV excitation due to the 5D4→7Fj (j = 6, 5, 4, 3) transition of Tb3+. Due to the large separation of Lu3+ ions in CNLBP structure lattice, the optimal concentration of Tb3+ is 80%, and concentration quenching occurs only for the full Tb3+ concentration.
2022, 41(2): 220214
doi: 10.14102/j.cnki.0254-5861.2011-3237
Abstract:
Persistent luminescence materials (PLMs) are potential luminescent materials which can remain emitting light after stopping the excitation. PLMs can avoid the autofluorescence of biological tissues, and play an important role in biosensing, targeted imaging and other fields. However, the applications of PLMs are often restricted by their weak persistent luminescence and short decay time after excitation. Doped ions will directly affect the luminescence centers and trap levels of PLMs, thereby leading to great differences in the optical performance of PLMs. Given this, the selection of doped ions to improve the optical performance of PLMs has become a fascinating research direction in recent years. At present, the published reviews mostly focus on the surface modifications and applications of PLMs. However, the influence of doped ions on the structure and optical performance of PLMs is seldom summarized. In this review, the influence of doped ions on the structure and optical performance of PLMs is introduced from three aspects: the type of doped ions, the number of types of doped ions, and the content of doped ions. Furthermore, we highlight recent achievements and mechanisms in the development of PLMs. Finally, we also propose and discuss the future opportunities and current challenges of ion-doped PLMs.
Persistent luminescence materials (PLMs) are potential luminescent materials which can remain emitting light after stopping the excitation. PLMs can avoid the autofluorescence of biological tissues, and play an important role in biosensing, targeted imaging and other fields. However, the applications of PLMs are often restricted by their weak persistent luminescence and short decay time after excitation. Doped ions will directly affect the luminescence centers and trap levels of PLMs, thereby leading to great differences in the optical performance of PLMs. Given this, the selection of doped ions to improve the optical performance of PLMs has become a fascinating research direction in recent years. At present, the published reviews mostly focus on the surface modifications and applications of PLMs. However, the influence of doped ions on the structure and optical performance of PLMs is seldom summarized. In this review, the influence of doped ions on the structure and optical performance of PLMs is introduced from three aspects: the type of doped ions, the number of types of doped ions, and the content of doped ions. Furthermore, we highlight recent achievements and mechanisms in the development of PLMs. Finally, we also propose and discuss the future opportunities and current challenges of ion-doped PLMs.
2022, 41(2): 220215
doi: 10.14102/j.cnki.0254-5861.2011-3280
Abstract:
In this report, a series of self-organized TiO2 nanotube arrays were prepared by anodization of titanium foil in mixed electrolytes composed of water, ethylene glycol, and NH4F. Their photoelectrochemical (PEC) performance as a photoanode was characterized by the PEC water-splitting hydrogen (H2) generation reaction. The internal relationship between the TiO2 nanotube arrays (TNTAs) morphology and their PEC performance was thoroughly investigated. Our results show that when the etching time is 10 hours, the length of the as-prepared TNTAs is about 20.78 μm and the measured photocurrent density is around 1.25 mA·cm-2 with applied bias voltage 0.6 V (vs. Ag/AgCl) under simulated sunlight irradiation, which is 976 times higher than that of the TiO2 substrate without nanotubes architecture (0.00128 mA⋅cm-2). More interestingly, the results of the IPCE measurement show that the band-gap of the as-prepared TNTAs is reduced from 3.20 to 2.83 eV. The corresponding optical response limit is also extended from 400 nm to TiO2 nanotube arrays is 510 nm, which indicates that the increasement of the TNTAs PEC performance benefits from the great improvement of its utilization of both the UV and visible light irradiation.
In this report, a series of self-organized TiO2 nanotube arrays were prepared by anodization of titanium foil in mixed electrolytes composed of water, ethylene glycol, and NH4F. Their photoelectrochemical (PEC) performance as a photoanode was characterized by the PEC water-splitting hydrogen (H2) generation reaction. The internal relationship between the TiO2 nanotube arrays (TNTAs) morphology and their PEC performance was thoroughly investigated. Our results show that when the etching time is 10 hours, the length of the as-prepared TNTAs is about 20.78 μm and the measured photocurrent density is around 1.25 mA·cm-2 with applied bias voltage 0.6 V (vs. Ag/AgCl) under simulated sunlight irradiation, which is 976 times higher than that of the TiO2 substrate without nanotubes architecture (0.00128 mA⋅cm-2). More interestingly, the results of the IPCE measurement show that the band-gap of the as-prepared TNTAs is reduced from 3.20 to 2.83 eV. The corresponding optical response limit is also extended from 400 nm to TiO2 nanotube arrays is 510 nm, which indicates that the increasement of the TNTAs PEC performance benefits from the great improvement of its utilization of both the UV and visible light irradiation.
2022, 41(2): 220207
doi: 10.14102/j.cnki.0254-5861.2011-3274
Abstract:
In this paper, a Cd(II) metal-organic framework (MOF), Cd-DIBT (HDIBT = 5-(3΄, 5΄-di(1H-imidazol-1-yl)-[1, 1΄-biphenyl]-4-yl)-1H-tetrazole), has been constructed based on a newly designed heterotopic tripodal ligand containing both imidazolyl and pyrazolyl groups. The Cd-DIBT exhibits a new three-dimensional (3, 3, 9)-connected trinodal network topology with point symbol of (42·6)(43)2(48·615·812·10) (namely scnu) based on binuclear secondary building blocks (SBUs). Staggered 1D channels were observed in such framework and was estimated to have 5487 Å3 potential solvent area (56%). The stability study reveals that the framework is unstable and easily transforms into amorphous MOF after the removal of guest molecules. In addition, the Cd-DIBT shows a ligand-centered luminescence.
In this paper, a Cd(II) metal-organic framework (MOF), Cd-DIBT (HDIBT = 5-(3΄, 5΄-di(1H-imidazol-1-yl)-[1, 1΄-biphenyl]-4-yl)-1H-tetrazole), has been constructed based on a newly designed heterotopic tripodal ligand containing both imidazolyl and pyrazolyl groups. The Cd-DIBT exhibits a new three-dimensional (3, 3, 9)-connected trinodal network topology with point symbol of (42·6)(43)2(48·615·812·10) (namely scnu) based on binuclear secondary building blocks (SBUs). Staggered 1D channels were observed in such framework and was estimated to have 5487 Å3 potential solvent area (56%). The stability study reveals that the framework is unstable and easily transforms into amorphous MOF after the removal of guest molecules. In addition, the Cd-DIBT shows a ligand-centered luminescence.
2022, 41(2): 220207
doi: 10.14102/j.cnki.0254-5861.2011-3277
Abstract:
A new 3D terbium(III) metal-organic network [Tb(HIMDC)(HCOO)(H2O)]n (complex 1) has been synthesized by Tb3+ ions coordinated with 4, 5-imidazole dicarboxylic acid (H3IMDC) and formic acid under solvothermal conditions with the mixed solvents of N, N-dimethylformamide (DMF) and H2O. The unambiguous structural determination has been confirmed by single-crystal X-ray diffraction combined with elemental analysis, infrared (IR) spectrum, thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Complex 1 crystallizes in orthorhombic Fdd2 space group with a = 22.295(2), b = 24.097(3), c = 6.7256(6) Å, V = 3613.3 Å3, Z = 16, Dc = 2.765 g/cm3, F(000) = 2816, μ = 7.855 mm-1, the final R = 0.0173 (I ≥ 2σ(I)), wR = 0.0416 (all data) and GOOF = 1.068. In complex 1, the Tb3+ ions are connected by HIMDC2- anions into 2D metal-organic layers which are further extended into a three-dimensional (3D) architecture through formic acid functional motif. In addition, complex 1 shows intense and characteristic green luminescence.
A new 3D terbium(III) metal-organic network [Tb(HIMDC)(HCOO)(H2O)]n (complex 1) has been synthesized by Tb3+ ions coordinated with 4, 5-imidazole dicarboxylic acid (H3IMDC) and formic acid under solvothermal conditions with the mixed solvents of N, N-dimethylformamide (DMF) and H2O. The unambiguous structural determination has been confirmed by single-crystal X-ray diffraction combined with elemental analysis, infrared (IR) spectrum, thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Complex 1 crystallizes in orthorhombic Fdd2 space group with a = 22.295(2), b = 24.097(3), c = 6.7256(6) Å, V = 3613.3 Å3, Z = 16, Dc = 2.765 g/cm3, F(000) = 2816, μ = 7.855 mm-1, the final R = 0.0173 (I ≥ 2σ(I)), wR = 0.0416 (all data) and GOOF = 1.068. In complex 1, the Tb3+ ions are connected by HIMDC2- anions into 2D metal-organic layers which are further extended into a three-dimensional (3D) architecture through formic acid functional motif. In addition, complex 1 shows intense and characteristic green luminescence.
2022, 41(2): 220209
doi: 10.14102/j.cnki.0254-5861.2011-3235
Abstract:
3, 4-Dichloro-5-(6-chloro-9-(4-fluorobenzyl)-9H-purin-8-yl)isothiazole, a novel purine derivative, was synthesized by the cyclization of pyrimidine amine. Its structure was characterized by 1H NMR, 13C NMR, 19F NMR, H RMS and single-crystal X-ray diffraction. This compound 3 is crystallized from a mixed solvent of dichloromethane and n-hexane (1:2, v/v) for structural identification as monoclinic crystal system, space group P21/n with a = 11.66250(10), b = 8.21300(10), c = 17.77920(10) Å, V = 1676.34(3) Å3, Z = 4, Dc = 1.643 g/cm3, F(000) = 832.0 and μ = 6.301 mm-1. 22315 reflections were measured (8.43≤2θ≤158.10°), of which 3532 were unique (Rint = 0.0311) and used in all calculations. The final R = 0.0334 (I > 2σ(I)) and wR = 0.0842 (reflections). The title compound showed over 50% of growth inhibition against Botrytis cinereal, Cercospora arachidicola, Gibberella zeae, Rhizoctonia solani and Sclerotinia sclerotiorum at 50 mg/L, and its EC50 value against R. solani was 60.44 µmol/L, which was active at the same level as that of positive control diflumetorim with its EC50 value of 60.29 µmol/L and less active than YZK-C22 with its EC50 value of 12.32 µmol/L, respectively. Our studies discovered that the combination of bioactive substructures of isothiazole with purine could be an effective way to novel fungicide development.
3, 4-Dichloro-5-(6-chloro-9-(4-fluorobenzyl)-9H-purin-8-yl)isothiazole, a novel purine derivative, was synthesized by the cyclization of pyrimidine amine. Its structure was characterized by 1H NMR, 13C NMR, 19F NMR, H RMS and single-crystal X-ray diffraction. This compound 3 is crystallized from a mixed solvent of dichloromethane and n-hexane (1:2, v/v) for structural identification as monoclinic crystal system, space group P21/n with a = 11.66250(10), b = 8.21300(10), c = 17.77920(10) Å, V = 1676.34(3) Å3, Z = 4, Dc = 1.643 g/cm3, F(000) = 832.0 and μ = 6.301 mm-1. 22315 reflections were measured (8.43≤2θ≤158.10°), of which 3532 were unique (Rint = 0.0311) and used in all calculations. The final R = 0.0334 (I > 2σ(I)) and wR = 0.0842 (reflections). The title compound showed over 50% of growth inhibition against Botrytis cinereal, Cercospora arachidicola, Gibberella zeae, Rhizoctonia solani and Sclerotinia sclerotiorum at 50 mg/L, and its EC50 value against R. solani was 60.44 µmol/L, which was active at the same level as that of positive control diflumetorim with its EC50 value of 60.29 µmol/L and less active than YZK-C22 with its EC50 value of 12.32 µmol/L, respectively. Our studies discovered that the combination of bioactive substructures of isothiazole with purine could be an effective way to novel fungicide development.
2022, 41(2): 220209
doi: 10.14102/j.cnki.0254-5861.2011-3232
Abstract:
A series of novel furan-1, 3, 4-oxadiazole carboxamide derivatives (5a~5e) were designed, synthesized and characterized by spectroscopic methods including HR-MS, 1H- and 13C-NMR. The crystal structure of compound 5a was determined by single-crystal X-ray diffraction. The compound crystallizes in the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A series of novel furan-1, 3, 4-oxadiazole carboxamide derivatives (5a~5e) were designed, synthesized and characterized by spectroscopic methods including HR-MS, 1H- and 13C-NMR. The crystal structure of compound 5a was determined by single-crystal X-ray diffraction. The compound crystallizes in the triclinic system, space group P
2022, 41(2): 220210
doi: 10.14102/j.cnki.0254-5861.2011-3246
Abstract:
Dibutyltin benzoin benzoyl hydrazone complex I [C6H5(O)C=N-N=C(Ph)CH(Ph)O]2[(n-Bu)2Sn]2 and dibutyltin benzoin salicyl hydrazone complex II [2-(OH)-C6H4(O)C=N-N=C(Ph)CH(Ph)O]2[(n-Bu)2Sn]2 were synthesized and characterized by IR, 1H, 13C and 119Sn NMR spectra, HRMS, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex I belongs to monoclinic system, space group P21/n with a = 11.1942(8), b = 10.4754(7), c = 23.6700(17) Å, β = 101.529(2)°, Z = 2, V = 2719.6(3) Å3, Dc = 1.371 Mg·m–3, μ(MoKα) = 0.966 mm–1, F(000) = 1152, R = 0.0458 and wR = 0.1312. The crystal of complex II is of triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
Dibutyltin benzoin benzoyl hydrazone complex I [C6H5(O)C=N-N=C(Ph)CH(Ph)O]2[(n-Bu)2Sn]2 and dibutyltin benzoin salicyl hydrazone complex II [2-(OH)-C6H4(O)C=N-N=C(Ph)CH(Ph)O]2[(n-Bu)2Sn]2 were synthesized and characterized by IR, 1H, 13C and 119Sn NMR spectra, HRMS, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex I belongs to monoclinic system, space group P21/n with a = 11.1942(8), b = 10.4754(7), c = 23.6700(17) Å, β = 101.529(2)°, Z = 2, V = 2719.6(3) Å3, Dc = 1.371 Mg·m–3, μ(MoKα) = 0.966 mm–1, F(000) = 1152, R = 0.0458 and wR = 0.1312. The crystal of complex II is of triclinic system, space group P
2022, 41(2): 220211
doi: 10.14102/j.cnki.0254-5861.2011-3249
Abstract:
Eighteen new acyl urea derivatives containing 2-chloronicotine moiety were synthesized using 2-chloronicotinic acid as starting material via 4 steps conveniently. These 2-chloronicotine acyl urea structures were confirmed by 1H NMR, 13C NMR and HRMS. Compound 4r was further confirmed by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 7.2960(3), b = 14.8546(6), c = 25.2840(11) Å, V = 2740.3(2) Å3, Z = 8, the final R = 0.0442 and wR = 0.1033 for 4028 observed reflections with I > 2σ(I). The antifungal activity results demonstrate that some of these compounds possessed good activity against B. cinerea, G. zeae, P. piricola, and P. Capsici at 50 ppm. Further molecular docking results indicated that the key group is urea bridge and pyridine ring.
Eighteen new acyl urea derivatives containing 2-chloronicotine moiety were synthesized using 2-chloronicotinic acid as starting material via 4 steps conveniently. These 2-chloronicotine acyl urea structures were confirmed by 1H NMR, 13C NMR and HRMS. Compound 4r was further confirmed by X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 7.2960(3), b = 14.8546(6), c = 25.2840(11) Å, V = 2740.3(2) Å3, Z = 8, the final R = 0.0442 and wR = 0.1033 for 4028 observed reflections with I > 2σ(I). The antifungal activity results demonstrate that some of these compounds possessed good activity against B. cinerea, G. zeae, P. piricola, and P. Capsici at 50 ppm. Further molecular docking results indicated that the key group is urea bridge and pyridine ring.
2022, 41(2): 220212
doi: 10.14102/j.cnki.0254-5861.2011-3256
Abstract:
To search for potential energetic materials with large energy density and acceptable thermodynamics and kinetics stability, twelve derivatives of 4-nitro-5-(5-nitro-1, 2, 4-triazol-3-yl)-2H-1, 2, 3-triazolate (named A~L) are designed and analyzed by using density functional theory (DFT) calculations at the B3LYP/6-311G** level of theory. The molecular heats of formation (HOF), electronic structures, impact sensitivity (H50), oxygen balance (OB) and density (ρ) are investigated by isodesmic reaction method and physicochemical formulas. Furthermore, the detonation velocity (D) and detonation pressure (P) are calculated to study the detonation performance by Kamlet-Jacobs (K-J) equation. These results show that new molecule J (H50 = 36.9 cm, ρ = 1.90 g/cm3, Q = 1912.46 cal/g, P = 37.82 GPa, D = 9.22 km/s, OB = 0.00), compound A (H50 = 27.9 cm, ρ = 1.93 g/cm3, Q = 1612.93 cal/g, P = 38.90 GPa, D = 9.19 km/s) and compound H (H50 = 37.3 cm, ρ = 1.97 g/cm3, Q = 1505.06 cal/g, P = 37.20 GPa, D = 9.01 km/s) present promising effects that are far better RDX and HMX as the high energy density materials. Our calculations can provide useful information for the molecular synthesis of novel high energy density materials.
To search for potential energetic materials with large energy density and acceptable thermodynamics and kinetics stability, twelve derivatives of 4-nitro-5-(5-nitro-1, 2, 4-triazol-3-yl)-2H-1, 2, 3-triazolate (named A~L) are designed and analyzed by using density functional theory (DFT) calculations at the B3LYP/6-311G** level of theory. The molecular heats of formation (HOF), electronic structures, impact sensitivity (H50), oxygen balance (OB) and density (ρ) are investigated by isodesmic reaction method and physicochemical formulas. Furthermore, the detonation velocity (D) and detonation pressure (P) are calculated to study the detonation performance by Kamlet-Jacobs (K-J) equation. These results show that new molecule J (H50 = 36.9 cm, ρ = 1.90 g/cm3, Q = 1912.46 cal/g, P = 37.82 GPa, D = 9.22 km/s, OB = 0.00), compound A (H50 = 27.9 cm, ρ = 1.93 g/cm3, Q = 1612.93 cal/g, P = 38.90 GPa, D = 9.19 km/s) and compound H (H50 = 37.3 cm, ρ = 1.97 g/cm3, Q = 1505.06 cal/g, P = 37.20 GPa, D = 9.01 km/s) present promising effects that are far better RDX and HMX as the high energy density materials. Our calculations can provide useful information for the molecular synthesis of novel high energy density materials.
2022, 41(2): 220213
doi: 10.14102/j.cnki.0254-5861.2011-3283
Abstract:
A series of 2, 4-diarylaminopyrimidine derivatives containing pyridine structure were designed and synthesized. The crystal structures of compounds 5d and 5e were obtained from X-ray diffraction. The crystal structure of 5d (C25H20ClFN6O2) belongs to the monoclinic system, space group P21/c with a = 11.0500(10), b = 18.3045(17), c = 13.5646(9) Å and β = 122.806(5)°. 5e (C25H19ClF2N6O2) is of monoclinic system, space group P21/c with a = 10.9998(18), b = 18.517(3), c = 13.6355(16) Å and β = 123.315(9)°. The bioassay results showed all of the target compounds exhibited potential antiproliferative activities against MKN-45, HT-29, A549, K562 and GIST882 cell lines. Among them, compounds 5a, 5c and 5e exhibited remarkable inhibitory activities against GIST882, K562 and A549 cell lines with IC50 values of 0.68, 0.38 and 0.60 μM, respectively, which were comparable to that of the positive control foretinib.
A series of 2, 4-diarylaminopyrimidine derivatives containing pyridine structure were designed and synthesized. The crystal structures of compounds 5d and 5e were obtained from X-ray diffraction. The crystal structure of 5d (C25H20ClFN6O2) belongs to the monoclinic system, space group P21/c with a = 11.0500(10), b = 18.3045(17), c = 13.5646(9) Å and β = 122.806(5)°. 5e (C25H19ClF2N6O2) is of monoclinic system, space group P21/c with a = 10.9998(18), b = 18.517(3), c = 13.6355(16) Å and β = 123.315(9)°. The bioassay results showed all of the target compounds exhibited potential antiproliferative activities against MKN-45, HT-29, A549, K562 and GIST882 cell lines. Among them, compounds 5a, 5c and 5e exhibited remarkable inhibitory activities against GIST882, K562 and A549 cell lines with IC50 values of 0.68, 0.38 and 0.60 μM, respectively, which were comparable to that of the positive control foretinib.
2022, 41(2): 220208
doi: 10.14102/j.cnki.0254-5861.2011-3341
Abstract:
With triazole-modified derivative as link, one new framework [Cd5(μ5-HL2-)2(μ4-L3-)2(H2O)10]·2H2O (1, H3L = 2-(1, 2, 4-triazol-1-yl)benzene-1, 3, 5-tricarboxylic acid) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction and elemental analysis. Complex 1 exhibits a 3D (3, 4, 6)-connected net cross-linked by binuclear [Cd2(COO)5]- cluster and mononuclear Cd(II) geometry via HL2-/L3- ligands. It crystallizes in triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
With triazole-modified derivative as link, one new framework [Cd5(μ5-HL2-)2(μ4-L3-)2(H2O)10]·2H2O (1, H3L = 2-(1, 2, 4-triazol-1-yl)benzene-1, 3, 5-tricarboxylic acid) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction and elemental analysis. Complex 1 exhibits a 3D (3, 4, 6)-connected net cross-linked by binuclear [Cd2(COO)5]- cluster and mononuclear Cd(II) geometry via HL2-/L3- ligands. It crystallizes in triclinic system, space group P
2022, 41(2): 220216
doi: 10.14102/j.cnki.0254-5861.2011-3260
Abstract:
A series of spinel LiAlxMn2-xO4 (x ≤ 0.1) cathode materials was synthesized by controlled crystallization and solid state route with micro-spherical Mn3O4 as the precursor. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to analyze the crystal structure of the synthetic material and the microscopic morphology of the particles. It was found that Al3+ doping did not change the spinel structure of the synthesized materials, and the particles had better crystallinity. In the charge and discharge test of the synthesized materials, we found that Al3+ doping would slightly reduce the discharge capacity, but it could effectively improve the cyclic stability of the material. The initial capacity of LiAl0.04Mn1.96O4 is 121.6 mAh/g. After 100 cycles at a rate of 1 C (1 C = 148 mA/g), the capacity can still reach 112.9 mAh/g, and the capacity retention rate is 96.4%. Electrochemical impedance spectroscopy (EIS) suggests that Al3+ doping can effectively enhance the diffusion capacity of lithium ions in the material.
A series of spinel LiAlxMn2-xO4 (x ≤ 0.1) cathode materials was synthesized by controlled crystallization and solid state route with micro-spherical Mn3O4 as the precursor. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to analyze the crystal structure of the synthetic material and the microscopic morphology of the particles. It was found that Al3+ doping did not change the spinel structure of the synthesized materials, and the particles had better crystallinity. In the charge and discharge test of the synthesized materials, we found that Al3+ doping would slightly reduce the discharge capacity, but it could effectively improve the cyclic stability of the material. The initial capacity of LiAl0.04Mn1.96O4 is 121.6 mAh/g. After 100 cycles at a rate of 1 C (1 C = 148 mA/g), the capacity can still reach 112.9 mAh/g, and the capacity retention rate is 96.4%. Electrochemical impedance spectroscopy (EIS) suggests that Al3+ doping can effectively enhance the diffusion capacity of lithium ions in the material.
