低分子量壳聚糖及其衍生物与金属离子配合物研究

Chitosan(CTS) of molecular weight 3 × 10⁶ was degraded by oxidation with H₂O₂. The molecular weight of degraded chitosan (CTS′) was between 5 500～6 000. Through the reaction of degraded chitosan with glyoxylic acid and sodium borohydride, the modified derivative of N-Carboxymethyl degraded chitosan (NCTS′) was obtained. The metal ions of Fe(Ⅱ), Ni(Ⅱ), Cu(Ⅱ) and Cr(Ⅲ) were coordinated at different conditions by degraded chitosan(CTS′ → M(Ⅱ)) and its derivative (NCTS′ →M(Ⅱ))). These coordination compounds were characterized with UV and IR spectroscopy.     

Cu(Ⅱ)-牛磺酸缩水杨醛席夫碱-邻菲咯林三元配合物的合成、晶体结构及性质

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. The crystal structure of the title complex belongs to orthorhombic system with space group Pbcn and cell parameters: a=3.107 2(4) nm, b=1.289 09(18) nm, c= 1.034 78(14) nm; and V=4.144 7(10) nm³, Z=8, D_c=1.596 g·cm^-3, μ=1.197 mm^-1, F(000)=2 048. The compound is an one-dimensional chain complex of infinite length which are connected with hydrogen bonds. The Cu(Ⅱ) was coordinated by two oxygen atoms and three nitrogen while the o atoms of Ac- groups did not participate in the coordination. The Cu(Ⅱ) formed a distorted tetragonal pyramid and the capacities of coordination to Cu(Ⅱ) of atoms was discussed. Besides, the TG-IR of the complex was analyzed. The kinetics of the thermal decomposition reaction of the complex was studied under a non isothermal condition by TG-IR. TG and DTG curves indicate that the complex decomposed in three stages: (?) The kinetic parameters were obtained from the analysis of TG,DTG cures by OZAWA-Flynn-Wall method, and the activation energy and the value of A of the three stages are 74.98 kJ·mol^-1, 286.65 kJ·mol^-1, 87.55 kJ·mol^-1; 9.66×10⁸ s^-1,1.82×10²⁸ s^-1, 3.09×10³s^-1, respectively.     

金属离子与卟啉的嵌入反应动力学研究——邻苯二甲酸缓冲溶液中溴化间-四(N-乙酸甲酯基-3-吡啶基)卟啉与Cu(Ⅱ)的配位反应

Kinetics of the coordination reaction of tetrakis(N-carbomethoxymethyl-3-pyridyl) porphyrin(abbr. H₂T_β-N-ACMSPyP) with Cu(Ⅱ) ion has been studied in o-phthalic acid buffer system in an ionic strength of 0.5mol·dm^-3(KCI) at 35.0±0.1℃.The reaction is catalyzed by o-phthalic ion. The effect of concentration of the cata-lyst, metal ion and pH value of solution was discussed. The kinetics equation of the reaction were obtained as d[CuP⁴⁺]/dt=16.15{(1.0+3.35×10⁵[PT^2-]²)/1.0+1.57×10^-4[H⁺]²}[Cu²⁺][P]_T. The mechanism of the reaction was proposed. The deformation of the ring of porphyrins is the general condition in the reaction.     

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.     

双核Cu(Ⅱ)-2，4-二羟基苯甲醛缩邻氨基苯甲酸Schiff碱配合物的合成、表征和晶体结构

The novel dinuclear copper(Ⅱ) complex with with N-(2，4-dihydroxybenzalidene)-o-aminobenzoic acid ligand， [Cu(C₁₄H₉NO₄)]₂·2H₂O， has been synthesized and characterized by elemental analysis， IR， UV-Vis and thermal analysis. Its crystal structure was determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The cell parameters are: a=0.82510(11)nm， b=0.68870(9)nm， c=2.3007(3)nm， β=100.847(2)°， V=1.2840(3)nm³， Z=2，D_c=1.742Mg·m^-3， μ(Mo Kα)=1.723mm^-1， F(000)=684. The structure was refined to final R₁=0.0267， wR₂=0.0735. The complex molecule structure has dinuclear centrosymmetric dimeric structure in which a planar Cu₂O₂ core features. The ligand N-(2，4-dihydroxybenzalidene)-o-aminobenzoic acid dianion is μ₂-tridentate， chelating one copper(Ⅱ) ion via one nitro-gen， one hydroxy oxygen atom and one carboxylate oxygen atom， and the hydroxy oxygen atom simultaneously co-ordinates to the other copper(Ⅱ) ion of the dimer. In the structure the copper(Ⅱ) ion rendered four-coordination in a distorted square-planar geometry structure. CCDC: 212695.     

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.     

二重穿插锰配合物Mn2(ADB)2(DMSO)4DMSO的溶剂热合成和结构研究

A novel Mn coordination polymers, Mn₂(ADB)₂(DMSO)₄·DMSO (H₂ADB=4,4′-azodibenzoic acid), has been prepared by solvothermal reaction and characterized by element analysis, IR spectra and single-crystal X-ray diffraction. The crystallographic data shows that the title complex crystallizes in monoclinic space group C2/c. Each Mn(Ⅱ) is six-coordinated to four O atoms from three ADB^2- ligands, two oxygen atoms from two DMSO molecule and forms distorted octahedral coordination geometry. The Mn(Ⅱ) dimers by the carboxyl groups of the ADB^2- ligands were interlinked together by the different carboxylate coordination modes of ADB^2- ligands, to yield scaffolds with 2D network with 4.8² topological structures. CCDC: 745678.     

配合物稳定性与酸碱强度之间的直线自由能关系——ⅪⅤ.N-(取代苯基)亚氨基二乙酸与铜(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)钴(Ⅱ)二元配合物的稳定性研究

The dissociation constants of N-(para-substituted phenyl) iminodiacetic acid (p-RPhID A, R= Cl, H, CH₃, CH₃O) and N-(ortho-substituted phenyl) iminodiacetic acid (o-RPhlDA) and the formation constants of binary complex compounds of Cu(Ⅱ)-o-RPhIDA, Cu(Ⅱ)-p-RPhIDA, Co(Ⅱ)-p-RPhIDA, Ni(Ⅱ)-p-RPhIDA and Zn(Ⅱ)-p-RPhIDA were determined by pH method in the presence 0.1mol·dm^-3KNO₃ at 25℃ . It has been found that linear free energy relationships not only exist between stability of these binary complex compounds and base strength of ligand, but also exist between logβ and σ'(=pK₂-pK₂).The deviation of Cu(Ⅱ)-o-CH₃PhIDA from linearity may be ascribed to steric effect of methyl group at ortho position.     

D201×4树脂对金(III)的吸附

Sorption behavior and mechanism of D201×4 resin for Au(III) were investigated. D201×4 resin has a good adsorptivity for Au(III) in HAc-NaAc medium at pH value of 2.63. The statically saturated Au(III) sorption capacity was 689.11 mg·g^-1 resin. The Au(III) adsorbed on D201×4 resin could be eluted by 10%NH₂CSNH₂-1 mol·L^-1 HCl(1∶1) and the elution rate was 92.2%.The adsorption of Au(III) on D201×4 follows the Freundlich isotherm. The ΔH of the adsorption was 11.03 kJ·mol^-1. The sorption rate constant was 5.42×10^-5 s^-1. The activation energy was 13.26 kJ·mol^-1. The molar coordination ratio of the functional group of D201×4 to Au(III) was about 1:1. The adsorption mechanism of resin for Au(III) was suggested according to chemical analysis and IR spectraoscopy results.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

LOW MOLECULAR WEIGHT O-CARBOXYMETHYLATED CHITOSANS DERIVED FROM IRRADIATED CHITOSAN AND THEIR ANTIBACTERIAL ACTIVITY*

 Original chitosan with M_v of 2.7 × 10⁵ was degraded by irradiation with γ-rays and a series of low molecular weight O-carboxymethylated chitosans (O-CMCh) were prepared based on the irradiated chitosan. A kinetic model of the irradiation of chitosan was put forward. Results show that the irradiation degradation of chitosan obeys the rule of random degradation and the degree of deacetylation of irradiated chitosan is slightly raised. The antibacterial activity of O-CMCh is significantly influenced by its MW, and a suppositional antibacterial peak appears when M_v is equal to 2 × 10⁵.     

壳聚糖锰(Ⅱ)配位与氧化控制降解寡糖的分子量分布

Complexes of chitosan with Mn(Ⅱ) were prepared by adding Mn(OAc)₂·4H₂O to Chitosan solution. IR, elemental analysis and TG analysis were used to character the complex. The results showed that there were coordinate bands formed. H₂O₂ was used to degrade chitosan-Mn(Ⅱ) complex, and the molecular distribution of degraded products were investigated after eliminating Mn(Ⅱ) ions using the cation exchange resin column. The result suggested that the Chitosan could be degraded rapidly, the degradation started from higher molecular weight range, the molecular weight distribution of oligosaccharides was much more narrower than that of degradated products from common methods such as hydrolysis, acidic and oxidizing methods. The index of molecular weight distribution was changed with the average degradability. When exceeding 10 oligosaccharides, the smaller of the DP, the smaller of the index.     

一个新颖三维配位聚合物Pb(1，4-napdc)(DMF)的合成、结构及热稳定性研究

A novel 3D metal-organic coordination polymer Pb(1,4-napdc)(DMF) (1,4-napdc=naphthalene-1,4-dicarboxylate) was synthesized at room temperature using slow vapor diffusion method to grow single crystal that has been analyzed by X-ray diffraction. The crystal belongs to orthorhombic with space group P2₁2₁2₁. The unit cell parameters are as fellows: a=0.701 3(2) nm, b=1.407 6(3) nm, c=1.521 5(4) nm, V=1.501 8(6) nm³ and Z=4. In the crystal structure of Pb(1,4-napdc)(DMF), the square grids constructed with paddle-wheel units of Pb(Ⅱ) and 1,4-napdc links stack over each other to generate infinite 3D network, which has square apertures (1.158×1.158 nm²) along the crystallographic a-axis. The thermal stability of compound was investigated by differential scanning calorimetry and thermogravimetric analysis. CCDC: 293617.     

邻苯二甲酸Pb(Ⅱ)配合物纳米颗粒的合成及其燃烧催化性能研究

The nanoparticle Pb(Ⅱ)-Phtalate complex was synthesized by liquid dispersion deposition method using Pb(Ac)₂·3H₂O and potassium acid phthalate as the reactant. The nanoparticle complexes were characterized with TEM, XRD, TG, DSC and IR. The composition of the nanoparticle PbPht complex was determined by chemical and elemental analysis. The catalytic performance of nanoparticle complex on the combustion of RDX-CMDB propellant was investigated. The results showed the average particle size of complex were about 50 nm. The nanoparticle Pb(Ⅱ)-Phtalate complex can enhance burning-rate of propellant by 135%, and lower the pressure exponent by 74%.     

一维聚合物{[Co(N3)2(dps)2]·0.5H2O}n的合成，结构和磁性质

A coordination polymer {[Co(N₃)₂(dps)₂]·0.5H₂O}_n (1) (dps=dipyridin-4-ylsulfane) with one dimensional chains has been synthesized and the structure and magnetic properties were characterized. Complex 1 crystallizes belongs to monoclinic system and has space group P2₁/c. The Co^Ⅱ ion is six-coordinated and located at a compressed octahedral environment due to the Jahn-Teller effect. The ligand of dps bridges between Co^Ⅱ ions producing the infinite chains of Co…Co along a direction and, interestingly, four pyridyl groups of dps ligands form a propeller-shaped coordination geometry around Co^Ⅱ ion with the same spiral within the chain. These 1D chains are further linked through the hydrogen bonds to generate a 3D supermolecular network. Magnetic studies indicated that complex 1 shows very weak antiferromagnetic coupling between Co^Ⅱ ions in low temperature. CCDC: 769596.     

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.     

一种确定固相反应机理函数的新方法——固态草酸镍(Ⅱ)二水合物脱水过程的非等温动力学

The dehydration of nickel(Ⅱ) oxalate dihydrate in solid state was investigated by TG-DTA techniques. On the basis of Coats-Redfern′s and Ozawa′s integral equations, the double extrapolate method was suggested, i.e.heating rate Φ and proportion weight loss of a sample α were extrapolated to zero, respectively. Using comparision E_Φ→0 with E_α→0 the kinetic mechanism was concluded to be nuclear producing and growing process (n=1.5). The intergral function of the mechanism is ［-ln(1-α)］^1/1.5 and the corresponding kinetic parameters were determined.     

配合物[Cu(HPHAc)2(py)2](H2PHAc=苯羟乙酸，py=吡啶)的合成和晶体结构

The novel copper(Ⅱ) complex with α-hydroxyphenylacetic acid (H₂PHAc) and pyridine (py) ligands, [Cu(HPHAc)₂(py)₂], has been synthesized and characterized by elemental analysis and IR spectroscopy. Its crystal structure was determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group C2/c. The cell parameters are: a=1.712 5(3) nm, b=1.533 2(2) nm, c=0.963 42(14) nm, β=111.866(2)°, V=2.347 6(6) nm³, and D_c=1.483 Mg·m^-3, Z=4, F(000)=1 084. The structure was refined to final R₁=0.071 4, wR₂=0.166 1. The complex has a six-coordinated distorted octahedral geometry, in which copper(Ⅱ) ion coordinates with two carboxylic oxygen atoms and two hydroxyl oxygen atoms from the two α-hydroxyphenylacetic acid ligands, two nitrogen atoms from the two pyridine ligands. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 255346.     

石英晶体微天平技术研究纳米TiO2表面Cu(Ⅱ)吸附与光化学还原过程

The adsorption and photochemical reduction process of Cu(Ⅱ) at the surface of nanocrystalline TiO₂ was investigated using in situ quartz crystal microbalance(QCM). It was found that the adsorption of Cu(Ⅱ) onto active sites of nanocrystalline fit the pseudo-second-order reaction better than the pseudo-first-order reaction, and that the rate constant of the reaction was estimated to be about 0.09 g·mmol₂·min₂. In addition, it was also found that the adsorption amount of Cu(Ⅱ) at the surface of TiO₂ was affected by pH、concentration and coexisting anions, and the saturated amount of adsorbed Cu(Ⅱ) was approximately 1.5 mmol·g^-1 at pH 4. During UV illumination, the frequency of QCM decreased gradually, which meant the photoreduction deposition of Cu(Ⅱ) from the solution, moreover, the rate of photodeposition of Cu(Ⅱ) increased with increasing pH of solution, and the rate of photoreduction enhanced obviously when the organics were introduced.     

Ni(Ⅱ)与Hbbimp配合物的合成、表征及晶体结构

A new complex with binuclear nickel(Ⅱ) complex [Ni₂(bbimp)(CH₃CH₂OH)₂Cl₂]Cl·4H₂O (bbimp=2，6-bis[bis(2-benzimidazolylmethyl)]aminomethyl-4-methylpheno)(o)had been synthesized and characterized by ele-mentary analysis， IR and UV. The molecular structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is monoclinic， space group P2₁/n with a=20.803(2)?， b=30.708(3)?， c=20.959(2)?， β=105.776(2)°， Z=8， V=12885(2)?³， D_x=1.132Mg·m^-3， μ=0.755mm^-1， F(000)=4592， R₁=0.1267， S=1.376. It was showed that the nickel(Ⅱ) cation is the central ion of a distorted octahedral coordination with two N belonging to benzimidazole， a bridging phenolate O， a N of tertiary amine， a Cl anion， and an O of an ethanol molecule. Two nickel(Ⅱ) cations in a molecular structure had the same coordinated environment. CCDC： 197601.