The continental margin of Northeast China and its adjacent areas is composed of two tectonic belts. The inner belt is a collage made up of fragments resulting from breakup of an old land with the north part related to...The continental margin of Northeast China and its adjacent areas is composed of two tectonic belts. The inner belt is a collage made up of fragments resulting from breakup of an old land with the north part related to the evolution of the Palaeo-Asian Ocean and the south part to the evolution of the Palaeo - Pacific Ocean. The outer belt is a Mesozoic terrane, which is a melange made up of fragments of the Late Palaeozoic to Early Mesozoic oceanic crust and the Late M esozoic trench accumulations.There existed another ocean-the Palaeo - Pacific Ocean during the period from the closing of the Palaeo-Asian Ocean to the opening of the modern Pacific Ocean or from the Devonian to Jurassic, and the ocean-floor spreading of the Palaeo - Pacific Ocean led to the formation of the above-mentioned tectonic belts. The development of the strike-slip fault system after the Late Jurassic and the formation of an epicontinental volcano -plutonic rock belt in the Late Cretaceous to Early Tertiary are attributed to the展开更多
A new complex Mn(Htpc)2(H2O)2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic ...A new complex Mn(Htpc)2(H2O)2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic system, space group P■ with a = 5.0885(10), b = 6.5574(13), c = 14.016(3) ?, β = 90.67(3)o, V = 436.34(17) ?3, Z = 1, Dc = 1.793 g·cm-3, μ = 0.855 mm-1, Mr = 471.18, F(000) = 235, the final R = 0.0454 and wR = 0.1134 for 1998 observed reflections with I > 2σ(I). The Mn(Ⅱ) ion is coordinated by two N and two O atoms from two Htpc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral coordinate geometry. The adjacent 0D units are linked into 1D chains through hydrogen bond O(1W)–H(1 WB)···O(2), and via the O(1 W)–H(1 WA)···O(1) hydrogen bond the neighboring 1D chains are connected into a 2D supramolecular layer. Moreover, the interactions between the ligand and its complex with CT-DNA were studied by EtBr fluorescence probe, which suggested that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.41 and 0.64 for Htpc and complex 1, respectively. It indicates that the interaction between complex 1 and CT-DNA is stronger than Htpc.展开更多
Zn(Ⅱ), Ni(Ⅱ) and Co(Ⅱ) compounds(1～3) based on 2-(2-pyridyl)benzothiazole(bpt) and terephthalic acid(PTA) were synthesized. The crystal structures of [Zn(bpt)(PTA)2](1), [Ni(bpt)(PTA)2](2), and [Co(bpt)(PTA)2](3) ...Zn(Ⅱ), Ni(Ⅱ) and Co(Ⅱ) compounds(1～3) based on 2-(2-pyridyl)benzothiazole(bpt) and terephthalic acid(PTA) were synthesized. The crystal structures of [Zn(bpt)(PTA)2](1), [Ni(bpt)(PTA)2](2), and [Co(bpt)(PTA)2](3) have been determined by single-crystal X-ray diffraction analysis, which shows that all the three complexes belong to monoclinic system with space group P21/c. Time-dependent density functional theory(TD-DFT) calculation is performed on a reference structure of compound 3. The excited electrons mainly localized at the π* of ligand 2-(2-pyridyl)benzothiazole, which will be convenient for them to bind with the DNA reacting sites. Fluorescence spectroscopy, ultraviolet(UV) spectroscopy and viscosity were used to characterize the interaction of the compounds with Calf thymus DNA(CT-DNA). The results indicate that compounds 1～3 bind to CT-DNA and have a strong interaction with DNA. The compounds can probably bind to CT-DNA via a non-intercalative mode as concluded by studying the viscosity of a DNA solution in the presence of the compounds. This combination can effectively break DNA, which speculates that these three compounds may interact with the cancer cell DNA in this binding mode, thereby damaging the cancer cells.展开更多
A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallograph...A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.展开更多
A novel copper(Ⅱ) complex with tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate(ampy) was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-m...A novel copper(Ⅱ) complex with tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate(ampy) was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper(II) complex with ampy, [Cu(ampy)Cl2](1), was formed irrespective of the metal-to-ligand molar ratios([Cu2+]:[ampy] = 0.5:1, 1:1, and 2:1) as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343(2), b = 18.928(3), c = 20.058(4) ?, V = 4686.1(14) ?3, Z = 8, Dc = 1.3349(4) g/cm^3, F(000) = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the central copper(II) ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H···Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory(DFT/B3LYP) method with the basis sets(6-31+G(d,p) for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively). The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital(NBO) analysis and frontier molecular orbitals(FMOs) analysis were investigated at the same level.展开更多
Two new Cd(Ⅱ) coordination polymers, [Cd(PT)(1,4-BDC)0.5]_n(1) and [Cd(PT)(1,3-BDC)0.5]_n(2)(HPT = 3-(pyridin-2-yl)-1,2,4-triazole, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid, 1,3-H2 BDC = 1,3-benzenedicarboxylic acid...Two new Cd(Ⅱ) coordination polymers, [Cd(PT)(1,4-BDC)0.5]_n(1) and [Cd(PT)(1,3-BDC)0.5]_n(2)(HPT = 3-(pyridin-2-yl)-1,2,4-triazole, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid, 1,3-H2 BDC = 1,3-benzenedicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Complexes 1 and 2 are both three-dimensional coordination polymers with two-dimensional sheet structures bridged by the deprotonated carboxylate ligands. In 1, 1,4-BDC^(2-) bridges the layered network to generate a quadrangular framework, and 2 owns a sexangular framework, which was caused by the different steric hindrance between 1,4-BDC^(2-) and 1,3-BDC^(2-). Their thermal stabilities and photoluminescent properties have been also investigated.展开更多
A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2...A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal 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 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.展开更多
The title compound, N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline(C16H15N3O2, Mr = 281.31), has been synthesized by the multicomponent reaction of milder Ullmann, and its structure was characterized by 1H NMR, 13 C NMR, I...The title compound, N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline(C16H15N3O2, Mr = 281.31), has been synthesized by the multicomponent reaction of milder Ullmann, and its structure was characterized by 1H NMR, 13 C NMR, IR, H RMS(ESI) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group I2/c with a = 15.0212(10), b = 9.4911(6), c = 20.3075(13) A, β = 100.776(7)o, V = 2844.1(3)A3, Z = 8, Dc = 1.314 g/cm3, F(000) = 1184.0, μ = 0.089 mm-1, the final R = 0.0574 and w R = 0.1688 for 1701 observed reflections(I > 2σ(I)). X-ray analysis indicates three major N(2)–H(2)···O(2), C(13)–H(13)···O(2), N(2)–H(2)···N(3) hydrogen bonds and π-π stacking interactions in the crystal structure. The preliminary biological test shows that the title compound has a good antitumor activity against A549 in vitro with the IC50 value of 35 μmol/L.展开更多
Two novel fluorine-containing cyclophanes 1 and 2 incorporating a 1,4-bismethylfluorophenylene subunits have been synthesized via the template-directed clipping methodology and their structure was characterized by 1H ...Two novel fluorine-containing cyclophanes 1 and 2 incorporating a 1,4-bismethylfluorophenylene subunits have been synthesized via the template-directed clipping methodology and their structure was characterized by 1H NMR, 13C NMR, MALDI-TOF-MS and elemental analysis. X-ray diffraction analysis of the solid state molecular structure showed that the complex units are linked by non-classical C-H…F hydrogen bonding.展开更多
An unusual two-dimensional supramolecular complex, namely, [Cd_2(Cl)_4(L)_2](1), has been synthesized by 2-(1 H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol(L) and CdCl_2·2.5H_2O under hydrothermal conditions. T...An unusual two-dimensional supramolecular complex, namely, [Cd_2(Cl)_4(L)_2](1), has been synthesized by 2-(1 H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol(L) and CdCl_2·2.5H_2O under hydrothermal conditions. The compound was characterized by elemental analysis, TG and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.151(2), b = 14.119(3), c = 14.744(3) ?, α = 115.744(4), β = 108.063(4), γ = 93.371(4)o, V = 1762.7(7) ?~3, Z = 2, C_(38)H_(24)Cd_2Cl_4N_8O_2, M_r = 991.25, D_c = 1.868 g/cm^3, F(000) = 976, μ(Mo Ka) = 1.560 mm^(-1), R = 0.0639 and w R = 0.1307. In 1, two Cd(II) atoms are bridged by two chroline atoms to give a dimer. Neighboring dimers are linked by N–H···Cl hydrogen bonds to afford supramolecular chains, which are further joined together by π-π interactions to result in a supramolecular layer. In addition, luminescent property and thermal behavior of compound 1 have been studied.展开更多
3-(Pyrrole-2?-carboxamido)propanoic acid I has been synthesized from the reaction of β-alanine methyl ester with 2-trichloroacetylpyrrole followed by saponifying and acidating in 85.4% yield, and the crystal structur...3-(Pyrrole-2?-carboxamido)propanoic acid I has been synthesized from the reaction of β-alanine methyl ester with 2-trichloroacetylpyrrole followed by saponifying and acidating in 85.4% yield, and the crystal structure of 3-(pyrrole-2?-carboxamido)propanoic acid· (1/2)H2O (C8H11N2O3.5, Mr = 191.19) was obtained and determined by X-ray diffraction method. The crystal is of monoclinic, space group C2/c with a = 19.010(4), b = 8.3515(17), c = 13.788(3) ?, β = 125.88(3)o, V = 1773.6(6) ?3, Z = 8, Dc = 1.432 g/cm3, λ = 0.71073 ?, μ(MoKα) = 0.114 mm?1 and F(000) = 768. The structure was refined to R = 0.0354 and wR = 0.0942 for 1642 observed reflections with I > 2σ(I). It is revealed that the title compound has one pyrrole ring and one propionic acid subchain linked by an amido bond at C(4), and there are 8 molecules of com- pound I and 4 crystal water molecules in each unit cell. The supramolecular layers are stabilized by the hydrogen bonds of N(2) H…O(2), N(1) H…O(4), O(4) H(1W)…O(2) and O(3) H…O(1).展开更多
A new dimeric Mn(Ⅱ) complex,namely,[Mn(L)(PIP)]_2·H_2O(1),was synthesized under hydrothermal condition(H_2L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and PIP = 2-(pyridin-3-yl)-1H-imidazo[4,5-f][1,10]phenant...A new dimeric Mn(Ⅱ) complex,namely,[Mn(L)(PIP)]_2·H_2O(1),was synthesized under hydrothermal condition(H_2L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and PIP = 2-(pyridin-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline).It crystallizes in triclinic,space group P1 with a = 9.2037(13),b = 9.6794(13),c = 14.649(3) ?,α = 94.858(3),β = 94.928(3),γ = 114.468(2)o,V = 1172.9(3) ?~3,Z = 1,C_(52)H_(34)Mn_2N_(12)O_(11),Mr = 1112.79,Dc = 1.575 g/cm^3,F(000) = 568,μ(Mo Ka) = 0.618 mm^(-1),R = 0.0432 and w R = 0.1151.In 1,two L anions bridge two Mn(Ⅱ) atoms to give a dimeric [Mn(L)(PIP)] unit with the Mn···Mn distance of 3.009(2) ?.The two PIP ligands are located on both sides of the dimer,which provides suitable π-π stacking interactions between PIP ligands.By these π-π stacking interactions,adjacent dimers are extended into a two-dimensional supramolecular layer.Further,the strong N–H···O hydrogen bond stabilizes the supramolecular layer structure of 1.Moreover,the thermal behavior and luminescent property of 1 have been studied.展开更多
A novel Zn(Ⅱ) complex, [ZnL_2(H_2O)_4]·H_2O(1, HL = 2-(nicotinoyloxy)acetic acid), was synthesized using Zn(OAc)_2·2H_2O and 2-(nicotinoyloxy)acetic acid as raw materials. Its structure has been elucidated ...A novel Zn(Ⅱ) complex, [ZnL_2(H_2O)_4]·H_2O(1, HL = 2-(nicotinoyloxy)acetic acid), was synthesized using Zn(OAc)_2·2H_2O and 2-(nicotinoyloxy)acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn(Ⅱ) atom is six-coordinated with two N atoms from two different 2-(nicotinoyloxy)acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-(nicotinoyloxy)acetic acid ligand and its Zn(Ⅱ) complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.展开更多
1-H-Pyrrole-2-carboxylic acid [2-(naphthalen-1-ylamino)-ethyl]-amide has been synthesized and characterized. Its crystal is of monoclinic, space group P21/n with a = 5.930(6), b = 12.144(13), c = 20.10(2) , β = 95.70...1-H-Pyrrole-2-carboxylic acid [2-(naphthalen-1-ylamino)-ethyl]-amide has been synthesized and characterized. Its crystal is of monoclinic, space group P21/n with a = 5.930(6), b = 12.144(13), c = 20.10(2) , β = 95.709(17)°, V = 1441(3) , Z = 4, C17H17N3O, Mr = 279.34, Dc = 1.288 g/cm3, F(000) = 592, μ(MoKα) = 0.083 mm-1, S = 1.019, R = 0.0473 and wR = 0.1181 for 1713 observed reflections with I > 2σ(I). X-ray diffraction reveals that two molecules of the title compound form a dimer through a pair of N–H…O hydrogen bonds.展开更多
The analytical structure of a typical fuzzy on - off controller that employs three or more triangular Input fuzzy sets, Zadeh fuzzy logic AND operator, fuzzy rules with singleton output fuzzy sets, and the centriod de...The analytical structure of a typical fuzzy on - off controller that employs three or more triangular Input fuzzy sets, Zadeh fuzzy logic AND operator, fuzzy rules with singleton output fuzzy sets, and the centriod defuzzifier is Investigated in this paper. The analytical expressions of the variable gains of the fuzzy controller are derived. The resulting explicit structure shows that the fuzzy controller is accurately a nonlinear PD - like controller with gains continuously changing with system output in different regions of input space.展开更多
The title compound (C40H42N2) has been synthesized by the reaction of 1-(1- naphthyl)-1-phenyl-3-chloropropylene and bis(4-(diethylamino) phenyl)methanone, and charac- terized by IR, 1H NMR, MS and X-ray diffraction a...The title compound (C40H42N2) has been synthesized by the reaction of 1-(1- naphthyl)-1-phenyl-3-chloropropylene and bis(4-(diethylamino) phenyl)methanone, and charac- terized by IR, 1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047(3), b = 10.807(2), c = 18.494(4) , β = 105.727(4)°, V = 3279.4(11) 3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm3, μ(MoKα) = 0.085 mm-1, F(000) = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections (I > 2σ(Ι)). X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4(2)° with the naphthalene ring.展开更多
The title compound C18H18N4OS has been synthesized by the reaction of 3-(2-hydroxy- benzyl)-4-amino-(1H)-1,2,4-triazole-5-thione with 4-isopropylbenzaldehyde in ethanol and characterized by IR, 1H NMR spectra and elem...The title compound C18H18N4OS has been synthesized by the reaction of 3-(2-hydroxy- benzyl)-4-amino-(1H)-1,2,4-triazole-5-thione with 4-isopropylbenzaldehyde in ethanol and characterized by IR, 1H NMR spectra and elemental analysis. Its structure was determined by X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 11.605(2), b = 7.401(1), c = 20.339(2) A, β = 103.05(2)°, V = 1701.8(4) ·3, Z = 4, Mr = 338.42, μ = 0.202 mm-1, Dc = 1.321 g/cm3 and F(000) = 712. The structure was solved by direct methods and refined to R = 0.0428 and wR = 0.1069. Due to the intramolecular O–H···N hydrogen bond and π-π stacking interactions between the benzene (C(1)～C(6)) and triazole rings, the two planes are essentially coplanar. Their biological activities have been measured, showing this type of compound has certain antibacterial activity for Staphylococous aureus and Bacillus subtilis. Based on the quantum chemistry calculation at the RHF/6-31G level, the frontier orbitals and electrostatic potential of the title compound were also discussed.展开更多
A quantitative method is developed to identify the structures of multi-layer woven fabric in this study. Six structural parameters are selected to represent the fabric structure. With some design criteria for the rein...A quantitative method is developed to identify the structures of multi-layer woven fabric in this study. Six structural parameters are selected to represent the fabric structure. With some design criteria for the reinforcement of textile composites, the relationships among the structural parameters are derived for different binding patterns of the fabric structure. The conditions, which meet the requirements of structural cell stability,are also discussed.展开更多
A new azopyrrole compound, 1, has been synthesized and characterized. The crystal of 1 is of monoclinic system, space group P21/c with a = 8.7167(9), b = 17.5929(19), c = 12.8096(15) ?, β = 97.565(2)o, V = 1947.3(4) ...A new azopyrrole compound, 1, has been synthesized and characterized. The crystal of 1 is of monoclinic system, space group P21/c with a = 8.7167(9), b = 17.5929(19), c = 12.8096(15) ?, β = 97.565(2)o, V = 1947.3(4) ?3, Z = 4, C_(20)H_(26)N_4O_2, Mr = 354.45, Dc = 1.209 g/cm^3, F(000) = 760 and μ(Mo Kα) = 0.080 mm^(-1). In the crystal, 1 binds one methanol molecule through N–H…O, O–H…O and O–H…π interactions. UV-Vis titration and 1H NMR titration studies reveal that compound 1 can selectively detect fluoride ion in the DMSO solution.展开更多
基金A Project supported by the National Natural Science Foundation of China (Nos.9487001,49173131)
文摘The continental margin of Northeast China and its adjacent areas is composed of two tectonic belts. The inner belt is a collage made up of fragments resulting from breakup of an old land with the north part related to the evolution of the Palaeo-Asian Ocean and the south part to the evolution of the Palaeo - Pacific Ocean. The outer belt is a Mesozoic terrane, which is a melange made up of fragments of the Late Palaeozoic to Early Mesozoic oceanic crust and the Late M esozoic trench accumulations.There existed another ocean-the Palaeo - Pacific Ocean during the period from the closing of the Palaeo-Asian Ocean to the opening of the modern Pacific Ocean or from the Devonian to Jurassic, and the ocean-floor spreading of the Palaeo - Pacific Ocean led to the formation of the above-mentioned tectonic belts. The development of the strike-slip fault system after the Late Jurassic and the formation of an epicontinental volcano -plutonic rock belt in the Late Cretaceous to Early Tertiary are attributed to the
基金Supported by the Scientific Research Foundation of Higher Education Institutions of Ningxia(No.NGY2017004)the National Natural Science Foundation of China(Nos.21763022 and 50564043)the Major Innovation Projects for Building First-class Universities in China’s Western Region(No.ZKZD2017003)
文摘A new complex Mn(Htpc)2(H2O)2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic system, space group P■ with a = 5.0885(10), b = 6.5574(13), c = 14.016(3) ?, β = 90.67(3)o, V = 436.34(17) ?3, Z = 1, Dc = 1.793 g·cm-3, μ = 0.855 mm-1, Mr = 471.18, F(000) = 235, the final R = 0.0454 and wR = 0.1134 for 1998 observed reflections with I > 2σ(I). The Mn(Ⅱ) ion is coordinated by two N and two O atoms from two Htpc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral coordinate geometry. The adjacent 0D units are linked into 1D chains through hydrogen bond O(1W)–H(1 WB)···O(2), and via the O(1 W)–H(1 WA)···O(1) hydrogen bond the neighboring 1D chains are connected into a 2D supramolecular layer. Moreover, the interactions between the ligand and its complex with CT-DNA were studied by EtBr fluorescence probe, which suggested that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.41 and 0.64 for Htpc and complex 1, respectively. It indicates that the interaction between complex 1 and CT-DNA is stronger than Htpc.
基金Supported by the Foundation for Jilin of China of 2014 Human Resources Developmentthe Natural Science Project Foundation of Education Department of Jilin Province(No.2015358)the Natural Science Foundation of Changchun Normal University(No.201203)
文摘Zn(Ⅱ), Ni(Ⅱ) and Co(Ⅱ) compounds(1～3) based on 2-(2-pyridyl)benzothiazole(bpt) and terephthalic acid(PTA) were synthesized. The crystal structures of [Zn(bpt)(PTA)2](1), [Ni(bpt)(PTA)2](2), and [Co(bpt)(PTA)2](3) have been determined by single-crystal X-ray diffraction analysis, which shows that all the three complexes belong to monoclinic system with space group P21/c. Time-dependent density functional theory(TD-DFT) calculation is performed on a reference structure of compound 3. The excited electrons mainly localized at the π* of ligand 2-(2-pyridyl)benzothiazole, which will be convenient for them to bind with the DNA reacting sites. Fluorescence spectroscopy, ultraviolet(UV) spectroscopy and viscosity were used to characterize the interaction of the compounds with Calf thymus DNA(CT-DNA). The results indicate that compounds 1～3 bind to CT-DNA and have a strong interaction with DNA. The compounds can probably bind to CT-DNA via a non-intercalative mode as concluded by studying the viscosity of a DNA solution in the presence of the compounds. This combination can effectively break DNA, which speculates that these three compounds may interact with the cancer cell DNA in this binding mode, thereby damaging the cancer cells.
基金Supported by the National Natural Science Foundation of China(No.21607051)Institute Foundation of Siping City(No.2017057)the Science and Technology Research Projects of the Education Committee of Jilin Province(No.JJKH20180779KJ)
文摘A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.
基金supported by the National Basic Research Program of China(No.2014CB643401)the National Natural Science Foundation of China(Nos.51134007 and 51474256)
文摘A novel copper(Ⅱ) complex with tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate(ampy) was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper(II) complex with ampy, [Cu(ampy)Cl2](1), was formed irrespective of the metal-to-ligand molar ratios([Cu2+]:[ampy] = 0.5:1, 1:1, and 2:1) as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343(2), b = 18.928(3), c = 20.058(4) ?, V = 4686.1(14) ?3, Z = 8, Dc = 1.3349(4) g/cm^3, F(000) = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the central copper(II) ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H···Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory(DFT/B3LYP) method with the basis sets(6-31+G(d,p) for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively). The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital(NBO) analysis and frontier molecular orbitals(FMOs) analysis were investigated at the same level.
基金supported by the National Natural Science Foundation of China(21501012 and 51203012)
文摘Two new Cd(Ⅱ) coordination polymers, [Cd(PT)(1,4-BDC)0.5]_n(1) and [Cd(PT)(1,3-BDC)0.5]_n(2)(HPT = 3-(pyridin-2-yl)-1,2,4-triazole, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid, 1,3-H2 BDC = 1,3-benzenedicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Complexes 1 and 2 are both three-dimensional coordination polymers with two-dimensional sheet structures bridged by the deprotonated carboxylate ligands. In 1, 1,4-BDC^(2-) bridges the layered network to generate a quadrangular framework, and 2 owns a sexangular framework, which was caused by the different steric hindrance between 1,4-BDC^(2-) and 1,3-BDC^(2-). Their thermal stabilities and photoluminescent properties have been also investigated.
基金supported by the Natural Science Foundation of Shaanxi Province(2018JQ2079,2018JQ2040,2018JM2055)
文摘A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal 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 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.
基金Supported by the National Natural Science Foundation of China(No.21576112)Natural Science Foundation Project of Jilin Province(No.20130521019JH and 20150623024TC-19)+1 种基金Natural Science Foundation Project of the Education Department of Jilin Province(No.[2014]152)the Science and Technology Development Plan of Siping City(2015049)
文摘Three lanthanide(III) complexes [Ln(4-NCP)(1,4-BDC)]n·xn H2O(Ln = Pr(1), Sm(2), Nd(3). 4-HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid) have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^(12)·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.
基金supported by the Fundamental Research Funds for the Central Universities(lzujbky-2010-137)Lanzhou Science and Technology Bureau Program Funds(2012-2-90)
文摘The title compound, N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline(C16H15N3O2, Mr = 281.31), has been synthesized by the multicomponent reaction of milder Ullmann, and its structure was characterized by 1H NMR, 13 C NMR, IR, H RMS(ESI) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group I2/c with a = 15.0212(10), b = 9.4911(6), c = 20.3075(13) A, β = 100.776(7)o, V = 2844.1(3)A3, Z = 8, Dc = 1.314 g/cm3, F(000) = 1184.0, μ = 0.089 mm-1, the final R = 0.0574 and w R = 0.1688 for 1701 observed reflections(I > 2σ(I)). X-ray analysis indicates three major N(2)–H(2)···O(2), C(13)–H(13)···O(2), N(2)–H(2)···N(3) hydrogen bonds and π-π stacking interactions in the crystal structure. The preliminary biological test shows that the title compound has a good antitumor activity against A549 in vitro with the IC50 value of 35 μmol/L.
基金support from the National Natural Science Foundation of China(No.20872051)
文摘Two novel fluorine-containing cyclophanes 1 and 2 incorporating a 1,4-bismethylfluorophenylene subunits have been synthesized via the template-directed clipping methodology and their structure was characterized by 1H NMR, 13C NMR, MALDI-TOF-MS and elemental analysis. X-ray diffraction analysis of the solid state molecular structure showed that the complex units are linked by non-classical C-H…F hydrogen bonding.
基金Supported by the National Natural Science Foundation of China(No.21607051)
文摘An unusual two-dimensional supramolecular complex, namely, [Cd_2(Cl)_4(L)_2](1), has been synthesized by 2-(1 H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol(L) and CdCl_2·2.5H_2O under hydrothermal conditions. The compound was characterized by elemental analysis, TG and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.151(2), b = 14.119(3), c = 14.744(3) ?, α = 115.744(4), β = 108.063(4), γ = 93.371(4)o, V = 1762.7(7) ?~3, Z = 2, C_(38)H_(24)Cd_2Cl_4N_8O_2, M_r = 991.25, D_c = 1.868 g/cm^3, F(000) = 976, μ(Mo Ka) = 1.560 mm^(-1), R = 0.0639 and w R = 0.1307. In 1, two Cd(II) atoms are bridged by two chroline atoms to give a dimer. Neighboring dimers are linked by N–H···Cl hydrogen bonds to afford supramolecular chains, which are further joined together by π-π interactions to result in a supramolecular layer. In addition, luminescent property and thermal behavior of compound 1 have been studied.
基金The project was supported by the National 863 Program of China(No.2004AA628030)Natural Science Foundation of Guangdong Province(No.31920)
文摘3-(Pyrrole-2?-carboxamido)propanoic acid I has been synthesized from the reaction of β-alanine methyl ester with 2-trichloroacetylpyrrole followed by saponifying and acidating in 85.4% yield, and the crystal structure of 3-(pyrrole-2?-carboxamido)propanoic acid· (1/2)H2O (C8H11N2O3.5, Mr = 191.19) was obtained and determined by X-ray diffraction method. The crystal is of monoclinic, space group C2/c with a = 19.010(4), b = 8.3515(17), c = 13.788(3) ?, β = 125.88(3)o, V = 1773.6(6) ?3, Z = 8, Dc = 1.432 g/cm3, λ = 0.71073 ?, μ(MoKα) = 0.114 mm?1 and F(000) = 768. The structure was refined to R = 0.0354 and wR = 0.0942 for 1642 observed reflections with I > 2σ(I). It is revealed that the title compound has one pyrrole ring and one propionic acid subchain linked by an amido bond at C(4), and there are 8 molecules of com- pound I and 4 crystal water molecules in each unit cell. The supramolecular layers are stabilized by the hydrogen bonds of N(2) H…O(2), N(1) H…O(4), O(4) H(1W)…O(2) and O(3) H…O(1).
基金Supported by the Institute Foundation of Siping city(No.2013036)
文摘A new dimeric Mn(Ⅱ) complex,namely,[Mn(L)(PIP)]_2·H_2O(1),was synthesized under hydrothermal condition(H_2L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and PIP = 2-(pyridin-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline).It crystallizes in triclinic,space group P1 with a = 9.2037(13),b = 9.6794(13),c = 14.649(3) ?,α = 94.858(3),β = 94.928(3),γ = 114.468(2)o,V = 1172.9(3) ?~3,Z = 1,C_(52)H_(34)Mn_2N_(12)O_(11),Mr = 1112.79,Dc = 1.575 g/cm^3,F(000) = 568,μ(Mo Ka) = 0.618 mm^(-1),R = 0.0432 and w R = 0.1151.In 1,two L anions bridge two Mn(Ⅱ) atoms to give a dimeric [Mn(L)(PIP)] unit with the Mn···Mn distance of 3.009(2) ?.The two PIP ligands are located on both sides of the dimer,which provides suitable π-π stacking interactions between PIP ligands.By these π-π stacking interactions,adjacent dimers are extended into a two-dimensional supramolecular layer.Further,the strong N–H···O hydrogen bond stabilizes the supramolecular layer structure of 1.Moreover,the thermal behavior and luminescent property of 1 have been studied.
基金supported by the National Natural Science Foundation of China(No.21171132)the Project of Shandong Province Higher Educational Science and Technology Program(J14LC01)Science Foundation of Weifang
文摘A novel Zn(Ⅱ) complex, [ZnL_2(H_2O)_4]·H_2O(1, HL = 2-(nicotinoyloxy)acetic acid), was synthesized using Zn(OAc)_2·2H_2O and 2-(nicotinoyloxy)acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn(Ⅱ) atom is six-coordinated with two N atoms from two different 2-(nicotinoyloxy)acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-(nicotinoyloxy)acetic acid ligand and its Zn(Ⅱ) complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.
基金The program was supported by University Science Foundation of TianjinEducational Committee (20050609) and Tianjin Normal University
文摘1-H-Pyrrole-2-carboxylic acid [2-(naphthalen-1-ylamino)-ethyl]-amide has been synthesized and characterized. Its crystal is of monoclinic, space group P21/n with a = 5.930(6), b = 12.144(13), c = 20.10(2) , β = 95.709(17)°, V = 1441(3) , Z = 4, C17H17N3O, Mr = 279.34, Dc = 1.288 g/cm3, F(000) = 592, μ(MoKα) = 0.083 mm-1, S = 1.019, R = 0.0473 and wR = 0.1181 for 1713 observed reflections with I > 2σ(I). X-ray diffraction reveals that two molecules of the title compound form a dimer through a pair of N–H…O hydrogen bonds.
文摘The analytical structure of a typical fuzzy on - off controller that employs three or more triangular Input fuzzy sets, Zadeh fuzzy logic AND operator, fuzzy rules with singleton output fuzzy sets, and the centriod defuzzifier is Investigated in this paper. The analytical expressions of the variable gains of the fuzzy controller are derived. The resulting explicit structure shows that the fuzzy controller is accurately a nonlinear PD - like controller with gains continuously changing with system output in different regions of input space.
基金The project was supported by the National 863 Program of China (No. 2002AA325050)
文摘The title compound (C40H42N2) has been synthesized by the reaction of 1-(1- naphthyl)-1-phenyl-3-chloropropylene and bis(4-(diethylamino) phenyl)methanone, and charac- terized by IR, 1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047(3), b = 10.807(2), c = 18.494(4) , β = 105.727(4)°, V = 3279.4(11) 3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm3, μ(MoKα) = 0.085 mm-1, F(000) = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections (I > 2σ(Ι)). X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4(2)° with the naphthalene ring.
基金This work was supported by the Natural Science Foundation of Zhejiang Province (No. M203115) and Scientific Research Fund of Zhejiang Provincial Education Department (No. 20050057)
文摘The title compound C18H18N4OS has been synthesized by the reaction of 3-(2-hydroxy- benzyl)-4-amino-(1H)-1,2,4-triazole-5-thione with 4-isopropylbenzaldehyde in ethanol and characterized by IR, 1H NMR spectra and elemental analysis. Its structure was determined by X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 11.605(2), b = 7.401(1), c = 20.339(2) A, β = 103.05(2)°, V = 1701.8(4) ·3, Z = 4, Mr = 338.42, μ = 0.202 mm-1, Dc = 1.321 g/cm3 and F(000) = 712. The structure was solved by direct methods and refined to R = 0.0428 and wR = 0.1069. Due to the intramolecular O–H···N hydrogen bond and π-π stacking interactions between the benzene (C(1)～C(6)) and triazole rings, the two planes are essentially coplanar. Their biological activities have been measured, showing this type of compound has certain antibacterial activity for Staphylococous aureus and Bacillus subtilis. Based on the quantum chemistry calculation at the RHF/6-31G level, the frontier orbitals and electrostatic potential of the title compound were also discussed.
文摘A quantitative method is developed to identify the structures of multi-layer woven fabric in this study. Six structural parameters are selected to represent the fabric structure. With some design criteria for the reinforcement of textile composites, the relationships among the structural parameters are derived for different binding patterns of the fabric structure. The conditions, which meet the requirements of structural cell stability,are also discussed.
基金supported by the National Natural Science Foundation of China(No.21172174)
文摘A new azopyrrole compound, 1, has been synthesized and characterized. The crystal of 1 is of monoclinic system, space group P21/c with a = 8.7167(9), b = 17.5929(19), c = 12.8096(15) ?, β = 97.565(2)o, V = 1947.3(4) ?3, Z = 4, C_(20)H_(26)N_4O_2, Mr = 354.45, Dc = 1.209 g/cm^3, F(000) = 760 and μ(Mo Kα) = 0.080 mm^(-1). In the crystal, 1 binds one methanol molecule through N–H…O, O–H…O and O–H…π interactions. UV-Vis titration and 1H NMR titration studies reveal that compound 1 can selectively detect fluoride ion in the DMSO solution.
