水杨醛酪氨酸铜配合物合成和EPR波谱

A new Schiff base derived from tyrosine and salicylidene and its copper(Ⅱ) complex have been synthesized and characterized by elemental analyses,molar conductances,thermal analyses,infrared spectra,electronic spectra and EPR spectra.The composition of the complex is K[CuL(Ac)]•H2O, where L=H13C16NO4. EPR spectra of the copper(Ⅱ) complex were investigated in various solvents at different temperatures.It is found that the linewidth of four hyperfine lines on solution spectra at room temperature is unequal and changes with mⅠ ,this could be satisfactorily explained by the relaxation effect.The relaxation time and the relaxation rate were calculated.By using spectral parameters from solution spectra at low temperature,the bonding parameters of Cu(Ⅱ) complex were calculated.The bonding characterization and stability of the complex were disscussed.The results show that the in plane 螵瞓ond and the in plane 皙瞓ond in the complex all play an important role.     

ESR spectra studies of Cu(Ⅱ) 2,4-dihydroxybenzaldehyde tyrosine complex

A novel Schiff base derived from 2,4-dihydroxybenzaldehyde and tyrosine and its copper(Ⅱ)complex have been synthesized and characterized.The composition of the complex is K[CuL] H2O,where L=H11C16NO5.ESR spectra of the copper(Ⅱ)complex were investigated at different temperatures and in various solvents.The second order effect and the relaxation effect were observed in the solution spectrum at room temperature,which was satisfactorily explained by spin Hamiltonian.The bonding parameters of copper(Ⅱ)complex were calculated using spectral parameters from ESR spectra at low temperature.Its bonding characterization and stability were disscussed.The result shows that the in-plane a-bond and the in-plane π-bond in the complex all play an important role.     

Crystal structure and single crystal EPR of (NH4)2(15-crown-5)3[Cu(mnt)2] and (NH4)2(benzo-15-crown-5)4[Cu(mnt)2]·0.5H2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2- anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(Ⅱ) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

5-氟尿嘧啶-1-乙酸合铜(Ⅱ)的合成及其与DNA的作用

The 5-fluorouracil-1-acetic acid (5FuAA) and its Cu(Ⅱ) complex (5FuAACu) were synthesized and the date for the crystal complex was obtained. The interaction of 5-fluorouracil-1-acetic acid (5FuAA) and its Cu(Ⅱ) complex (5FuAACu) with DNA was also investigated by using spectral, viscometric, electrochemical and agarose gel electrophoresis methods. The results of interaction with DNA suggest that both 5FuAA and 5FuAACu can bind to DNA in a static electricity attraction mode. But the attraction of 5FuAACu is greater than that of 5FuAA.     

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.     

Effect of Nano-anatase TiO2 on Spectral Characterization of Photosystem Ⅱ Particles from Spinach

The photosystem Ⅱ (PS Ⅱ ) particles were purified by means of nano-anatase TiO2 treatment of spinach and studied by spectroscopy. The results show that the electron transport and the oxygen-evolving rate of PS Ⅱ are accelerated after it has been treated with nano-anatase TiO2; the UV-Vis absorption spectrum of PS Ⅱ particles is increased; the red shift of fluorescence emission peak of PS Ⅱ is 2 nm; the peak intensity is decreased; the PS Ⅱ signal Ⅱ s of low temperature electron paramagnetic resonanace(EPR) spectrum is intensified under light, and the PS Ⅱ circular dichroism(CD) spectrum is similar to that of control. It is suggested that nano-anatase TiO2 might bind to the PS Ⅱ reaction center complex and intensify the function of the PS Ⅱ electron donor, however, nano-anatase TiO2 treatment does not change the configuration of the PS Ⅱ reaction center complex.     

ANALYSIS OF FRAGMENT INTERACTION AND ASSIGNMENT OF ELECTRONIC SPECTRUM FOR COMPLEX ION[S2MoS2FeCl2]^2—

<正> The electronic structures of complex ion [S2MoS2FeCl2]2- (1) and its fragments MoS42- (2) and FcCl2(3) have been calculated base on the LCAO-HFS method with restricted open shell or closed shell. The interaction between the fragments 3 and 2 and the formation of complex ion 1 have been discussed. It was found that the Fe(Ⅱ) donated electrons to the Mo(Ⅵ)and accepted electrons from the sulphur ligand and that the stability of complex ion 1 is contributed from both direct and indirect interactions through the bridging sulphur atoms. In addtion, the electron transition energies of complex ion 1 were calculated and its electronic absorptions were assigned. It was shown that the calculated wavelengths of the absorption bands are in agreement with the observed ones.     

Synthesis and relaxivity of Gd(Ⅲ), Fe(Ⅲ) and Mn(Ⅱ) complexes with dihydropyridine derivative of diethvlenetriaminepentaacetic acid

A novel ligand of DTPA-dihydropyridine derivative was synthesized by reaction of DTPA-dianhydride with 4-aniline-1,4-dihydropyridine. Its complexes of gadolinium, manganese and iron were prepared. Their spin-lattice relaxivities (T1) were investigated. The results show that the NMR T1 relaxivitives (R1) for complexes of Fe(Ⅲ), Mn(Ⅱ) are less than that of Gd(Ⅲ) complex, which has a high relaxivity (R1) on the surrounding water protons, indicating that the Gd(Ⅲ) complex possesses the precondition to be contrast agents for magnetic resonance imaging.     

N530-OT-煤油-HCl反萃分散组合液膜体系迁移和分离铜的研究

The transport and separation of copper(Ⅱ) from waste water by a N₅₃₀-OT-kerosene-HCl strip dispersion hybrid liquid membrane system was studied. The influence of penetrant OT, N₅₃₀ concentration, pH in feed phase, membrane area, HCl concentration in stripping phase, and volume ratio of membrane phase to stripping phase on transport and separation were also investigated. The experiments demonstrate that Cu(Ⅱ) can be transported selectively from the binary Cu(Ⅱ) and Fe(Ⅲ) solution to stripping phase and that the transport percentage of Cu(Ⅱ) exceeds 93.8% and Fe(Ⅲ) is only 1.8% after transport of 6 hours.     

二维氢键层状Mg(Ⅱ)配合物的合成、晶体结构及其抗菌活性(英文)

A new complex hexaaquamagnesium(Ⅱ) bis [2-(thiosemicarbazonomethyl)-benzoato],has been prepared and characterized by elemental analysis,IR spectra,molar conductivity and single-crystal X-ray diffraction. The results of crystal structure show that each Mg(Ⅱ) ion is coordinated with six oxygen atoms from water molecules and the complex formed two dimensional layered structure through intramolecule and intermolecule hydrogen bonds. The antibacterial assay of the magnesium(Ⅱ) complex and the ligand were tested using a modified version of the 2-fold serial dilution method,the results show that the complex show considerable antibacterial activity against escherichia coli,bacillus subtilis and staphylococcus white,and the ligand did not show antibacterial activity.     

Structure and Photosynthetic Mimicking of Bis（2,6—bis（benzimidazol—2—yl）pyridine）manganese（Ⅱ）

Mn(bzimpy)2(1)[bzimpy=2,6-bis(benzimidazol-2-yl)pyridine],a mononuclear manganese(Ⅱ）complex,was synthesized by the reaction of Mn(OOCMe)2 with bzimpy in absolute ethanol.The complex was structurally characterized by elemental analysis,cyclic voltammetry,and X-ray crystallography.In the complex,the manganese-nitrogen distances were different,and the geometry and the metal ion environment showed the distortion.The cyclic voltammetric measurements have been performed to assess its redox characteristics.The presence of oxidation wave at 0.62V and 0.081V vs.SCE or 0.8V and 1.0v vs.NHE suggested that this complex could catalyze the oxidation of water,therefore,simulate the water-oxidizing complex(WOC) of photosystem Ⅱ (PS Ⅱ).The measurements of photoreduction of 2,6-dichlorophenolindophenol (DCPIP),and oxygen evolution in the manganess-depleted and the comples 1-reconstituted PS Ⅱ preparations just support our conjecture.     

Preparation and Identification of Angelica sinensis Polysaccharide-iron Complex

Angelica sinensis polysaccharide(ASP) was extracted from Angelica sinensis by boiling water. An Angelica sinensis polysaccharide-iron complex(APC) was prepared under the alkaline condition by adding a ferric chloride solution to the ASP solution. Then some identifiable properties of the complex were studied. The content of iron (Ⅲ) in the complex was determined with iodometry. The thermal property, the microscopic structure, the spectral characteristics, and N, C, H contents of the complex were examined by a variety of techniques including DSC, TEM, IR,NMR, and elemental analysis. The content of iron (Ⅲ) in the complex ranges from 10% to 40%. The DSC result shows that the melting point of the complex is about 450 ℃. The TEM result shows that the complex has an iron(Ⅲ)core(β-FeOOH core) linked by hydroxy and oxy bridges, with the polysaccharide chains attached to the surface of the core. The IR and NMR results also show that there is aβ-FeOOH core in the complex. The elemental analysis shows that the contents of N, C , H in the complex are, respectively, lower than those of N, C, H in ASP. All our studies indicate that the APC consists of aβ-FeOOH core surrounded by ASP.     

Structures and Spectroscopic Properties of(1)Dipyridine Quinoxaline with Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ)

The interaction of Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ) with dipyridine quinoxaline ligand 2,3-bis(2-pyridyl)quinoxaline(DPQ) were investigated, and three new complexes have been synthesized and characterized. Complex 1 exhibits a 0D dual-core structure, complex 2 is a 0D tetra nuclear case based on a dual-core Cu unit, and complex 3 shows a one-dimensional pipeline structure. Furthermore, the optical properties of complex and DPQ were also investigated, and the results showed that the fluorescence intensity of complexes was weaker than that of ligand DPQ.     

Investigation of Mixed Chiral Selectors of Different Metal Ion-L-Alanine Complex and β-Cyclodextrin on the Chiral Separation of Dansyl Amino Acids with Capillary Electrophoresis

Chiral separation of dausyl amino acids by capillary electrophoresis using mixed selectors of Mn(ll)-L-alanine complex and β-cyclodextrin (β-CD) was studied. Resolution was considerably superior to that obtained by using either Mn (Ⅱ)-L-alanine complex or β-CD alone. The effects of separation parameters, such as pH value of buffer solution, capillary temperature, the concentration of Mn (Ⅱ)-L-alanine complex, the types of CD and ligand on the migration times and resolutions were investigated. Six different transition metal complexes,Cu(Ⅱ), Zn(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Hg(Ⅱ) and Cd(Ⅱ)-L-alanine complexes have been employed and compared with Mn(Ⅱ)complex. Differences in retention and selectivity were found.The substitution of Cu(Ⅱ), Zn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) for Mn(Ⅱ) resulted in a better chiral resolution while Hg(Ⅱ) and Cd(Ⅱ) showed poorer resolution abilities. The chiral separation mechanism was also discussed briefly.     

STRUCTURE AND PROPERTIES OF COMPOSITE POLYURETHANE HOLLOW FIBER MEMBRANES

Composite polyurethane (PU)-SiO2 hollow fiber membranes were successfully prepared via optimizing the technique of dry-jet wet spinning, and their pressure-responsibilities were confirmed by the relationships of pure water fluxtransmembrane pressure (PWF-TP) for the first time. The origin for this phenomenon was analyzed on the basis of membrane structure and material characteristics. The effects of SiO2 content on the structure and properties of membrane were investigated. The experimental results indicated that SiO2 in membrane created a great many interfacial micro-voids and played an important role in pressure-responsibility, PWF and rejection of membrane: with the increase of SiO2 content, the ability of membrane recovery weakened, PWF increased, and rejection decreased slightly.     

Crystal structure and single crystal EPR of (NH_4)_2(15-crown-5)_3[Cu(mnt)_2] and (NH_4)_2(benzo-15-crown-5)_4[Cu(mnt)_2]·0.5H_2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2? anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(II) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

Phase Chemistry and Thermochemstry on Coordination Behavior of Zinc Chloride with Leucine

The solubility property of the ZnCl2-Leu-H2O(Leu=L-a-leucine) system at 298.15K in the whole concentration range was investigatey by the semimicro-phase equilibrium method.The corresponding solubility diagram and refractive index diagram were constructed.The results indicated that there was one complex formed in this system.namely,Zn(Leu)Cl2.The complex is congruently soluble in water.Based on Phase equilibrium data,the complex was prepared.Its composition and properties were characterized by chemical analysis,elemental analysis,IR spectra,and TG-DTG.The thermochemical properties of coordination reaction of zinc chloride with L-a-leucine were investigated by a microcalorimeter.The enthalpies of solution of L-a-leucine in water and its zinc complex at infinite dilution and the enthalpy change of solid-liquid reaction wrer determined at 298.15K.The enthalpy change of soild phase reaction and the standard enthalpy of formation of zinc complex were claculated.On the basis of experimental and calculated results,three thermodynamic parameters(the activation enthalpy,the activation entropy and the activation free energy),the rate constant and three kinetic parameters(the activation energy,the preexponential constant and the reaction order) of the reaction,and the standard enthalpy of formation of Zn(Leu)^2 (aq) were obtained.The results showed that the title reaction took place easily at studied temperature.     

STUDY ON NOVEL SORBENT FOR REMOVAL OF UREA COMPLEX SORPTION OF UREA BY MEANS OF ALGINATE—Cu（Ⅱ） COMPLEX

Alginate-Cu(Ⅱ）complex beads or membranes were prepared for removal of urea.The mechanism of sorption of urea was identified by UV-Visible spectra,FT-IR spectra and Far-Infrared spectra.The factors affecting the urea sorption capacity were discussed in detail.Results showed that the Alginate-Cu(Ⅱ）complex sorbent can sorb about 60 my urea per gram of sorbent at 37℃ and the concentration of urea was 130mg/100ml in Na2HPO4 and NaH2PO4 buffer solution(pH=7.0).     

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%.     

不同构象铂(Ⅱ)配合物与G-肌动蛋白作用的光谱研究

The cyclohexamethylene-diamine squaric acid platinum(Ⅱ) complexs(R,R, S,S) binding to G-actin and the consquence conformation change were studied by N-(1-pyrenyl) maleimide(NPM) labeled fluorescence and intrinsic fluorescence. The binding and chemical kinetics were determined by fluorometry. The results showed that when R (Pt/actin molar ratio) was lower than 30, the Pt binded to G-actin strong binding sites(-SH), when R was larger than 30, the Pt binded to G-actin weaker binding sites. The consquence conformation changes were determined by CD. The CD results showed that R was smaller than 60, G-actin α-helix contents decreased slowly, R was larger than 60, G-actin conformation changed obviously. The reaction of R,R complex of platinum(Ⅱ) S,S complex of platinum(Ⅱ) with G-actin was similar to that of with S,S complex of platinum(Ⅱ).