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However, the thermal stability of metallic coordination polymer hardly enhanced in comparison with the polymer never coordinated transitional metallic ions. The reason might be that the energy of coordinate bond formed between metallic ion and polymer was trival in comparison with that of covalent bond in polymer. It started with coordinate bond when the coordinate polymer decomposed under high temperature, so it engendered little for the thermal stability at high temperature.

而金属配聚物较未配位金属的配体高温热稳定性提高不大,可能是由于金属离子与配体之间形成配位键的键能与配位体内的共价键键能相比要小得多,当金属配聚物受热裂解时,首先从配位键开始,因此对高温热稳定性的影响甚微。

Cu and Co ions are coordintated with six oxygen atoms from two water molecules and four ligands to form an octahedral geometry. Each ligand links two metal ions in a μ2-bridge coordination mode and two-dimensional wavelike structures are formed.

Cu和Co均为六配位,八面体构型,每个金属离子与4个配体和2个水分子配位,每个配体采取μ2-桥联模式,形成二维层状结构。

The results showed that the mole ratio of three ligands to CoCl_2, NiCl_2 were 1:1 and to CuCl_2, ZnCl_2, CdCl_2 were 2:1, The IR, UV-Vis and FS of complexes were investigated. Their IR peaks were classified as the corresponding groups or bonds; The relation of their structure with the conjugative effects, absorbtion wavelength and molar absorb coefficients were discussed with the UV-Vis and FS.

结果表明:噻唑类配体与金属CuCl_2,CdCl_2配位比分别2∶3和3∶2,至于配位机理还需进一步探讨;硒二唑配体与CoCl_2和NiCl_2配位比均是1∶1,而与CuCl_2、ZnCl_2和CdCl_2的配位均为比2∶1;对配合物的IR吸收峰进行了归类与指认,并对配合物的紫外和荧光光谱进行讨论分析,推测硒二唑类化合物与金属发生配位的部位是v中Se原子与金属配位。

Furthermore, the one-dimensional complexes 26 and 28 with strongπ-πpacking interactions are prepared from DMF solvent, which indicates that the traditional solvent volatilizing method could bring low-dimensional complex.4. By measuring the enthalpy changes of the liquid phase formation reaction for complexes a~e, and calculating the electronic densities of five 5-substituted derivation of isophthalic acid, we can make a conclusion that 5-substituted group changing of the ligand has a little influence on oxygen atoms of carboxyl groups.5. Fluorescence experiments of these complexes indicated that they could be used for luminescence materials in future.6. Using packing saturation rule we calculated and analyzed these series of complexes, and the results showed that the changes of complexes with changes of ligands could be explained from the rule.

在DMF溶剂中得到了具有强π-π堆积作用力的一维配位聚合物[Ln(5-NO_2-bdc)(NO_3)]Ln=Pr(26和Ho(28),表明传统的溶剂挥发合成条件可以得到低维的配合物。4、通过配合物a~e的液相生成反应焓的测定,以及配体阳离子的电子密度计算,进一步佐证了间苯二甲酸的5位取代基变化对配体的羧基氧原子配位能力影响不大的结论。5、荧光特性表明此类配合物可以用于发光材料。6、利用堆积饱和规律对所得系列的配合物的进行计算和分析,发现随着配体的变化,配合物的变化可以从堆积饱和规律出发进行解释。

The first part is to synthesize 5-formyl -8- quinolinol from 8-uinolinol and chloroform , using ethanol as a solvent. Then analysizing the 5-formyl-8-quinolinol by IR. The second part is , according to ideas of molecule designing, to synthesize the new self-assembly Inorganic-Organic coordination polymers Co(u2-bpyV2O6,(C4H4N2)Ni2(H2O)2-V4Ol2,(Cl2Hl2N2)Co-V2O6 using Cu, Ni, and Co as templating, 4-cyano-pyridine(4-CNPy), 4,4-bipyridine,pyrazine, l,2-bis(4-pyridyl)ethane, 5-formyl -8- quinolinol as building blocks and Ammonium Metavanadate (NH4VO3) as subordinate building blocks by Hydrothermal , analysizing their content of element determining their structures by X-Ray diffraction.

本课题实验分为两部分:一是配体的合成,以8-羟基喹啉、三氯甲烷为原料,以乙醇为溶剂,合成了5—甲醛基—8羟基喹啉并且对其进行了IR的分析测定;二是配位聚合物的合成,通过分子设计,采用溶剂热法以Cu、Ni、Co为中心离子,以5—甲醛基—8羟基喹啉、4,4-联吡啶、吡嗪、1,2-二吡啶基乙烷为配体,以偏钒酸根(VO_3~-)为辅助配体,通过水热法自组装合成了新的3-D网状结构配位聚合物Co(μ_2-bpy)V_2O_6,(C_4H_4N_2)Ni_2(H_2O)_2·V_4O_(12),C_(12H_(12)N_2Co·V_2O_6,并对其进行了元素分析和晶体结构的测定。

In order to get the information of interaction between metal complex and DNA and select metal complexes which can cleave DNA effectively, twenty seven transition metal complexes containing O/N coordinate atoms have been synthesized in this thesis. We report the synthesis, crystal structure and properties of the complexes. One of the complexes is the first μ〓-oxalato tetranuclear Cu complex, in which there is ferromagnetic interaction between the copper atoms bridged by oxalate ions. Two trinuclear copper complexes containing partial cubane Cu〓O〓 cores have been synthesized and discussed the magnetic properties.

为了解金属配合物与DNA的相互作用及筛选能有效切割DNA的金属配合物,为无机药物合成及应用提供基础信息,本文利用十个含N、O原子的多齿配体设计合成了二十七个未见文献报道的过渡金属配合物,并解析了它们的晶体结构:其中包括首例μ〓-草酸根的四核铜配合物;合成了两个具有μ〓-OH〓三核缺角立方烷结构的Cu配合物;以HCBP衍生物为配体合成了七个过渡金属配合物;以SCN〓、N〓,C〓O〓等为桥联配体,以dmpyen为端基配体合成了十一个配合物。

Four bidentate NS ester ligands, two bidentate NS amide ligands, tridentate MBPA and tetradentate BMBPA ligands have been synthesized.

合成了四种含有酯基的NS二齿配体-CYE系列物,两种含有酰胺基的NS二齿配体,三齿配体MBPA和四齿配体BMBPA。

The carboxyl of the tripodal ligand is a goodbridging group. The building blocks are linked together by the bridging group andother weak interactions (hydrogen bond and π-π stacking interaction, etc), thusgenerating a one, two or three-dimensional metal complexes.2. Studies on the fluorescence properties of the lanthanide complexes indicated that:(1) The excitations in the ligand-based π-π〓 transitions cause the structuredemission of lanthanide complexes while the ligand luminescence is completelyquenched showing that ligand-to-metal energy transfer occurs.

三脚架配体所带的羧基是一个很好的桥联基团,配合物的结构基元通过这种基团的桥联作用及其它一些弱的作用力(如氢键、π-π堆积作用等)联系起来,构成了一维、二维或三维的超分子空间结构。2、稀土配合物的发光研究发现:(1)用配体的π-π〓跃迁波长进行激发,配合物均显示出稀土离子的特征发射峰,同时,配体的荧光峰没有出现,这说明在三脚架配体与稀土离子间进行了有效的能量传递。

However, fully consideration of special structure and physiological function of CRP is critical to investigate whether CRP provide protect effect or pathogenic effect in the progression of atherosclerosis. CRP is a member of pentrxins family, which consists of five identical, noncovalently associated 23-kDa protomers arranged symmetrically around a central pore with a 102 A external diameter. Each protomer has a recognition face with a phosphocholine binding site consisting of two coordinated calcium ions adjacent to a hydrophobic pocket. The opposite face of the pentamer is the effector face, where complement Clq binds and Fc receptors are presumed to bind. A cleft extends from the center of the protomer to the central pore of the pentamer. Both faces ofpentamer form a special bi-phase structure: one face is the ligand recognition phase, which can recognize apoptosis cells and enzyme modified low density lipoprotein in which PCh is exposed.

CRP是一种五聚体蛋白,外径为102 A,由5个相同的单体以非共价键结合,形成双面的环形结构,每个单体的配体识别位点或受体结合位点分别位于五聚体两个平面上,分别组成配体识别相和效应器相,从而构成特殊的二相性结构:一面为配体识别相,含有磷酸胆碱(phosphorycholine,PCh)结合位点,能够使CRP识别在病理条件下暴露出PCh的凋亡细胞、酶修饰低密度脂蛋白(enzyme modified low density lipoprotein,E-LDL)等。E-LDL是天然低密度脂蛋白(native Low density lipoprotein,N-LDL)在多种蛋白酶,如胰蛋白酶、神经氨酸酶、胆固醇酯酶等作用下的代谢产物,其主要特点是结构发生改变(N-LDL大小均匀,平均直径250±30 A,E-LDL大小差异极大,直径为100-2000 A),暴露磷酸胆碱位点,能够被CRP识别;另一面为效应器相,能够与巨噬细胞、单核细胞表面受体FcγRⅡa结合,介导巨噬细胞、单核细胞识别及吞噬凋亡、坏死细胞作用。

After the completion of reaction, ether is added to the resulting mixture to precipitate the tartrate and filter to recover the ligand. The recovered ligands keep good enantioselectivity only in first recycle, but compared with solution-phase of tartrate counterpart, using of soluble polymer-supported tartrates largely simplifies the workup of sharpless epoxidation.

反应完成后,向反应体系中加入乙醚使配体沉淀,过滤即可回收配体,虽然回收的配体只在第一次循环中保持了较好的对映选择性,但与使用小分子酒石酸酯配体相比,使用可溶性聚合物支载的酒石酸酯极大地简化了Sharpless环氧化反应的后处理。

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