Cu(Ⅱ)-牛磺酸缩水杨醛席夫碱配合物的合成及晶体结构

The title complex was synthesized by reaction of taurine salicylic schiff base(TSSB), O-phenanthroline(phen) and cupric acetate in water-ethanol solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 498.00. And the crystal structure belongs to orthorhombic system with space group Pbcn and cell parameters: a=31.072(4)?, b=12.8909(18)?, c=10.3478(14)?; V=4144.7(10)?³,Z=8,D_c=1.596Mg·m^-3,μ=1.197mm^-1 and F(000)=2048. The compound is an one-dimensional chain complex of infinite length connecting with hydrogen bonds. The Cu(Ⅱ) was coordinated by two oxygen atoms and three nitrogen while the O atoms of Ac- groups did not coordinate. At the same time the Cu(Ⅱ)formed a distorted tragonal cone. Besides the capacities of coordination to Cu(Ⅱ) of atoms were discussed.     

复盐法制备无水氯化镁的热解机理及动力学研究

The complex compound (MgCl₂·C₆H₅NH₂·HCl·6H2O) was prepared by reaction of C₆H₅NH₂·HCl with MgCl₂·6H₂O. Reaction mechanism and kinetics of the compounds decomposition were studied by means of the TG-DTA-MS coupling technique and the TG-DTA technique. The results show that there are four steps in the complex′s thermal decomposition, the first two steps correspond to the loss of six crystal waters and the last two steps loss one Aniline hydrochloride. The first three steps belong to the R2 mechanism with 2-dimentional phase boundary reaction as the control step, and the last step belongs to the D3 with 3-dimensional diffusion (sphere Jander equ.) as the control step. The apparent active energy of four steps are, 127.4 kJ·mol^-1, 124.8 kJ·mol^-1, 142.3 kJ·mol^-1 and 329.0 kJ·mol^-1, respectively and the frequency factor are 1.28 × 10¹⁸ s^-1, 7.94 × 10¹⁵ s^-1, 5.98 × 10¹⁶ s^-1 and 4.39 × 10³⁴ s^-1, respectively.     

杂多酸盐K7[PTi2W10O40]·6H2O与牛血清白蛋白相互作用的研究

Under the imitated physiological condition of animal body, the interactions of heteropoly salt (PM-19) with bovine serum albumin (BSA) were investigated by fluorescence and absorption spectroscopy. It was shown that this compound had a quite strong ability to quench the fluorescence launching from BSA. After analyzing the fluorescence quenching data according to Stern-Volmer equation and Lineweaver-Burk double-reciprocal equation, we found that BSA had reacted with PM-19 and formed a certain new compound. The quenching belonged to static fluorescence quenching. According to Lineweaver-Burk equation, the forming constants of the compound (298 K: 2.68 × 10⁵ L·mol^-1; 304 K: 2.19 × 10⁵ L·mol^-1; 310 K: 1.82 × 105 L·mol^-1) and the thermodynamic parameters (ΔH=-24.72 kJ·mol^-1; ΔS=20.97 J·mol^-1·K^-1 / 20.92 J·mol^-1·K^-1/ 20.97 J·mol^-1·K^-1; ΔG=-30.97 kJ·mol^-1/ -31.08 kJ·mol^-1/-31.22kJ·mol^-1) at the corresponding temperatures were obtained. The latter shows that binding power between them is mainly electrostatic interaction. Based on F?rster′s non-radiation energy transfer mechanism, the binding locality (r=4.14 nm) was calculated between donor and accepter. The effect of PM-19 on the conformation of BSA was also analyzed by synchronous fluorescence spectroscopy.     

配合物[Mn(bipy)3](ClO4)2的晶体结构和热分析研究

The complex [Mn(bipy)₃]·(ClO₄)₂ was synthesied and characterized by X-ray diffraction. X-ray diffraction result for the single crystal showed that the crystal belongs to triclinic, space group P1, a=0.8123(2),b=1.1024(2), c=1.8646(4)nm,α=102.30(3)°,β=91.00(3)°,γ=99.69(3)°,V=1.6056(6)nm³,Z=2,D_c=1.494g·cm^-3. The thermal decomposition of [Mn(bipy)₃](ClO₄)₂ occurred in a three steps pattern. The reaction mechanism of the first step decomposition was deduced as n(1-α)[-ln(1-α)](n-1)/n with the activation energy of 130kJ·mol^-1.     

夹层化合物四氯合镉(Ⅱ)酸4-硝基苯铵的合成与结构

The title compound was prepared by the solid state reaction of stoichiometric amounts of CdCl₂·H₂O and 4-nitroaniline . The crystal used for X-ray analysis was obtained by slow evaporation of an ethanol-aqueous solution of the solid state reaction at room temperature. The structure of compound was characterized by X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbca, a=0.77864(7)nm,b=0.72547(6)nm,c=3.3126(2)nm,Z=4,V=1.8712(3)nm³,D_c=1.890g·cm^-3,μ=1.763mm^-1, F(000)=1048,R=0.0300,wR=0.0697. The title compound is a typical two-dimensional organic intercalated compound. The inorganic layers of the compound are formed by CdCl₆ octahedra sharing corner Cl atoms (i.e. catena-poly[dihlorocadmium-di-μ-chloro]). The organic ammonium cations are intercalated between every two metal-halogen layers and formed the organic layers of the compound through hydrogen bonding.     

二聚体[Ni(TSSB)(Phen)(H2O)]·4H2O的合成、表征、晶体结构及热分解研究

The new compound, [Ni(TSSB)(Phen)(H₂O)]·4H₂O (TSSB=Taurine Salicylic Schiff Base, phen=O-Phenanthroline) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The compound crystal data: triclinic, space group P1, a=1.049 7(2), b=1.122 5(2), c=2.384 3(4) nm, α=87.676(3)°, β=82.957(3)°, γ=62.924(3)°; V=2.482 3(7) nm³, Z=4; D_c=1.488 g·cm^-3, μ=0.920 mm^-1, F(000)=1 160, Goof=1.032, (Δρ)_max=899 e·nm^-3, (Δρ)_min=-624 e·nm^-3. The compound is a dimmer. In the complex, two Ni(Ⅱ) were coordinated by three oxygen atoms and three nitrogen atoms while the O atoms of Ac^- groups did not coordinate. The Ni(Ⅱ) formed a distorted octahedron geometry. The compound is an three dimensional net connecting with hydrogen bonding. CCDC: 275474.     

一维链状4-硝基-3-羧甲基苯异丙酸镉配位聚合物{[Cd(3-CNPP)(Py)3]·2H2O}n的合成、晶体结构及热稳定性研究

A novel one-dimensional coordination polymer, {[Cd(3-CNPP)(Py)₃]·2H₂O}_n (3-CNPP^2-=2-(3-carboxymethyl-4-nitrophenyl)propionate dianion, Py=pyridine) was synthesized and characterized by the element analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in monoclinic system with space group P2₁/ n, a=0.974 81(19) nm, b=1.992 3(4) nm, c=1.459 8(3) nm, β=95.92(3)°, and V=2.820 0(10) nm³ Z=4, R=0.037 3, wR=0.083 8. Each cadmium(Ⅱ) atom is seven-coordinated by four oxygen atoms from two different 3-CNPP^2- groups and three nitrogen atoms from three pyridine ligands, forming a distorted pentagonal bipyramindal coordination geometry. The cadmium(Ⅱ) atoms are bridged by the tetradentate 3-CNPP^2- groups, constructing a one-dimensional zigzag chain structure along c axis. The adjacent distance of Cd…Cd atoms is 0.979 6 nm. The two-dimensional hydrogen-bonding supramolecular network was formed via the hydrogen bond interactions. CCDC: 254257.     

CH2(COO)2Cu·2H2O热分解的非等温动力学研究

The thermal dehydration and decomposition kinetics of CH₂(COO)₂Cu·2H₂O were investigated using the non-isothermal method by thermogravimetry (TG) technique in N₂. The iterative iso-conversional methods were applied to calculate the activation energy E_a of dehydration and decomposition， and the most probable mechanism function G(α) was determined by means of the master plots method. The pre-exponential factor A was obtained on the basis of E_a and G(α). Kinetic parameters (E_a and lnA) of dehydration were given as: E_a=139.79 kJ·mol^-1， ln(A/s^-1)=47.38. The mechanism function of the dehydration was G(α)=[-ln(1-α)]^2/3， and the decomposition of CH₂(COO)₂Cu proceeds to completion by two distinct reactions. These two reactions overlap in the transition process (0.45<α<0.65). Kinetic parameters (E_a and lnA )of the first reaction of decomposition were: E_a=201.15 kJ·mol^-1， ln(A/s^-1)=52.29， and the mechanism function was G(α)=[1-α]^-0.37. And in the second reaction G(α)=α+(1-α)ln(1-α)， E_a=156.74 kJ·mol^-1， ln(A/s^-1)=39.58.     

锆-氘反应热力学特性研究

The p-c-T curves and the relation between equilibrium pressure and temperature of deuterium absorption and desorption from zirconium were measured in the temperature range of 400～675 ℃. Equilibrium pressure of the absorption and desorption at different temperatures were given and then the thermodynamic parameters and the deuterium absorption capacity were determined according to Vant Hoff equation. There are different changes of enthalpy and entropy when zirconium changes to different phases. The change of enthalpy in the phase of α plus δ is -98.9 kJ·mol^-1 in the temperature range of 400～475 ℃. The changes of enthalpy in the first and second plateau are -75.1 kJ·mol^-1 and -161.7 kJ·mol^-1, respectively in the temperature range of 525～675 ℃. The corresponding changes of entropy are -66.5 J·K^-1·mol^-1, -32.4 J·K^-1·mol^-1 and -146.5 J·K^-1·mol^-1, respectively. There are obvious lagging effects when zirconium desorbs deuterium.     

穴状Schiff碱配合物［Gd(NO3)·L］(NO3)2的晶体结构

A new mononuclear gadolinium complex ［Gd(NO₃)·L］(NO₃)₂ of Schiff base cryptand was obtained by condensation of tris (2-aminoethyl)amine with 2,6-diformyl phenol in template procedure. The complex was characterized by elemental analysis, IR, and x-ray single crystal diffraction analysis. Gadolinium is nine-coordinate in trigonal tricapped prism with five oxygen atoms from three phenols and a bidentate nitrate group, and four nitrogen atoms from three imino C=N bonds and a tertiary amine in the cryptand. The complex crystallized in triclinic system space group P1, a=1.0839(2) nm, b=1.2600(4) nm, c=1.7595(4) nm, α=82.09(2)°, β=89.22(2)°, γ=84.06(2)°， V=2.367(2) nm³, Z=2.     

配位聚合物[Mn(4，4′-bpy)1.5(H2O)3](ClO4)·(4，4′-bpy)(L)·H2O的水热合成和晶体结构

The title compound, [Mn(4,4′-bpy)_1.5(H₂O)₃](ClO₄)·(4,4′-bpy)(L)·H₂O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°, γ=91.118(2)°, V=1.884 0(4) nm³, Z=2, M_r=780.10, D_c=1.375 g·cm^-3, μ=0.483 mm^-1, F(000)=812, R=0.055 4, wR=0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4′-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4′-bipyridine molecules. CCDC: 615707.     

高岭石无定形化的动力学研究

Amorphous kaolinite derivatives were prepared through mixing kaolinite with HCOOK and KOH solution. Ki-netics of kaolinite being turned into amorphous derivatvies was investigated by XRD. It showed that the transfor-mation included dynamic and diffuse controlling stages. And the active energy E₁=26.8kJ·mol^-1; E₂=12.2 kJ·mol^-1. TEM and SEM images showed that particle size of the amorphous derivatives was about 50nm. And the amorphous derivatives seemed like alumnsilicate gel， accompanied by some aggregates.     

L-苏糖酸锰的制备及标准生成焓

The pink powder of manganese L-threonate was obtained by extracting with alcohol the concentrated solution derived from the reaction between L-threonic acid solution prepared by double decomposition reaction of calcium L-threonate with oxalic acid and superfluous manganese oxide at 80℃ for certain time. The composition of the new compound was determined by chemical and elemental analyses and its formula fits Mn(C₄H₇O₅)₂·H₂O, the IR spectra indicated that Mn²⁺ in the compound coordinates to oxygen atom of the carboxyl group, while the proton of the carboxyl group is dissociated, it was assumed that the coordination number of Mn²⁺ was 4. The results of TG-DTG showed that the compound have fairish stability, the intermediate and final product of the thermal de-composition of the compound are Mn(C₄H₇O₅)₂ and MnO₂, respectively. The constant volume combustion energy of the compound, Δ_cE, were determined by a precise rotating-bomb calorimeter at 298.15K, it was (-3384.30±1.21)kJ·mol^-1, its standard enthalpy of Combustion,Δ_cH_m^?,and standard enthalpy of formation,Δ_fH_m^? , were calculated. They are (-3383.07±1.21)kJ·mol^-1 and (-2 571.68±1.63)kJ·mol^-1, respectively.     

壳聚糖/Pb(Ⅱ)模板壳聚糖膜与Pb(Ⅱ)螯合反应的动力学及机理探讨

Chitosan and chitosan membranes with Pb(Ⅱ) ion as template were studied. The adsorption isotherms were correlated by dc/dt=-kcⁿ at the temperature of 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃. By means of linear correlation, the shapes of the isotherm curves were similar to the kinetic function of 2/c^1/2=-kt and the apparent activation energy for with chitosan(123.8 kJ·moL^-1) was larger than that of membrane with Pb(Ⅱ) ion(92.3kJ·moL^-1). The chitosan membrane with Pb(Ⅱ) ion template was better “memory” function. The adsorption mechanism of chitosan with Pb(Ⅱ) was studied by IR and XPS. The results indicated that the nitrogen in -NH₂ and the oxygen in C₃-OH of chitosan were coordination atoms.     

一维链状2-氧-1(4H)-吡啶乙酸桥联钙配位聚合物[Ca(2-OPA)2(H2O)2]n的合成、晶体结构及热稳定性研究

A novel coordination polymer of [Ca(2-OPA)₂(H₂O)₂]_n (2-OPA-=2-oxo-1(4H)-pyridineacetate anion) was synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in orthorhombic with space group Pna2₁, a=0.799 96(16) nm, b=0.823 77(16) nm, c=2.415 3(5) nm, V=1.591 6(6) nm³, Z=4, R=0.030 3, wR=0.070 0. The Ca atom is eight-coordinated by six O atoms of four 2-OPA^- ligands and two water molecules, and displays a dodecahedron coordination geometry. Each 2-OPA^- ligand bridges two adjacent Ca atoms, forming a infinite chain along the a direction. The Ca…Ca distance is 0.4102 2(8)nm. A two-dimensional supramolecular framework is further constructed by the hydrogen bonds and the weak π-π interactions. The results of TG analysis show the chain structure of the title complex was stable under 297.5 ℃. CCDC: 251669.     

[Zn(py)2SHSH]的合成、晶体结构及理论研究

The crystal of zinc complex with salicylaldehyde salicylhydrazone(SHSH) was obtained in DMF and pyridine. It has been characterized by IR, UV, element analysis and X-ray diffraction analysis. The crystallographic data were as follows: monoclinic system, space group Pn, a=1.094 6 nm, b=0.884 0 nm, c=1.161 0 nm, β=101.350°, Z=2, V=1.101 0 nm³, D_c=1.441 g·cm^-3, μ=1.148 mm^-1, F(000)=492 and the final R=0.029 5 and wR=0.068 5 for 2 642 observed reflections with I≥2σ(I). The X-ray crystal structure analysis revealed that the center zinc(Ⅱ) is bonded to two oxygen atoms and one nitrogen atoms from a tridentate ligand(SHSH) and two nitrogen atoms from two solvent pyridine molecules to form a five-coordinate distorted trigonal bipyramid. The full-optimized molecular geometries of title complex was calculated at B3LYP/6-31G and HF/6-31G levels with Guassian 98W program. CCDC: 252832.     

钾的N-酰化牛磺酸配合物的合成、表征及其晶体结构

The title complex(K(C₉H₁₃NO₅S₂)(H2O)) was synthesized by the reaction of p-tolysulfonyl chloride, taurine and potassium hydrate in water-methanol-ethanol solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 336.44. The crystal structure of the title complex belongs to orthorhombic space group Pbca and cell parameters: a=0.853 31(12) nm, b=0.820 42(12) nm, c=3.989 4(6) nm. V=2.792 8(7) nm³, Z=8, D_c=1.600 g·cm^-3, μ=0.699 mm^-1, F(000)=1 400. The compound is an one-dimension chain complex of infinite length which are connected with hydrogen bond and bridging coordination water. The difference and same of the complexes were discussed. CCDC: 244938.     

配合物[Cu2(phen)2](SiW12O40)(H2O)7的合成、晶体结构及电化学分析

The title complex has been synthesized by the reaction of silicotungstic acid, 1,10-phenanthroline (phen) monohydrate and cupric acetate. The crystal structure belongs to triclinic system, space group P1 with a=1.158 46(15) nm, b=1.658 8(2) nm, c=1.664 4(2) nm, α=82.090(2)°, β=76.001(2)°, γ=86.531(2)°, and V=3.072 6(7) nm³, D_c=3.887 g·cm^-3, Z=2, F(000)=3 196. R₁=0.086 7, wR₂=0.185 8. The structure shows that the copper(Ⅱ) atom is coordinated with two nitrogen atoms from the one phen and three oxgygen atoms from three water, forming a distorted square-pyramid configuration The cyclic voltametric behavior of the complex is also reported. CCDC: 298807.     

一种有机-无机电荷转移配合物的合成、结构及性能研究

A charge-transfer complex, [(C₂H₄OH)₃NH]₂·[HPMo₁₂O₄₀]·3H₂O, has been synthesized and characterized.The crystal structure of the complex was determined by X-ray diffraction. It belongs to orthorhombic, space grounp Pnna, with a=1.541 30(5) nm, b=1.884 23 (7) nm, c=2.049 06(7) nm, α=β=γ=90.00°, V=5.950 8(4) nm³, Z=4, D_c=2.427 Mg·m^-3 , F(000)=4 132, μ(Mo Kα)=2.568 mm^-1. The structure was refined to R₁=0.043 5 and wR₂=0.122 4 by full-matrix least-squares method. The O atoms of the polyoxometalate, the C atoms of the organic substrates and the O atoms of water molecules are involved in hydrogen bonding. Spectral data support the presence of an electronic interaction between the organic substrate and the inorganic anion in the solid state. It is strongly photochromic under ultraviolet light resulting from charge-transfer. The electrochemical behavior of the compound shows that the redox peak currents are proportional to the scan rate in pH=4.0 NaAc-HAc buffer solution, which indicates that the electrode reaction are surface controlled processes.     

亚氨基二乙酸树脂吸附钇(Ⅲ)的研究

The adsorption behavior and mechanism of a novel chelate resin, iminodiacetic acid resin (IDAAR) for Y(Ⅲ) were investigated. The statically saturated adsorption capacity is 102mg·g^-1 resin at 298K in HAc-NaAc medium at pH 5.7. Y(Ⅲ) adsorbed on IDAAR can be reductively eluted by 1.0～4.0mol·L^-1 HCl used as eluant and the elution percentages are almost as high as 100%. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k₂₉₈=3.36×10^-5s^-1. The adsorption behavior of IDAAR for Y(Ⅲ) conforms to Freundlich′s model reasonably. The thermodynamic adsorption parameter, enthalpy change ΔH of IDAAR for Y(Ⅲ) is 18.6kJ·mol^-1. The complex molar ratio of the functional group of IDAAR to Y(Ⅲ) is about 3∶1. The adsorption mechanism of IDAAR for Y(Ⅲ) was examined by using chemical method and IR spectrometry.