含肽键（-CONH）芳酰腙、1，10-菲啰啉与稀土配合物的研究

【作者】 杨锐；

【导师】 何水样； 文振翼；

【作者基本信息】 西北大学 ， 化学， 2004， 硕士

【摘要】 在水醇混合溶剂中，以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄，H₃L)及1，10-菲啰啉(C₁₂H₈N₂，phen)与稀土（RE=La、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Yb、Lu和Y）的硝酸盐反应，合成了12种未见文献报道的配合物，经元素分析、IR、UV、FS、¹H NMR等表征并结合热分析确定了配合物的组成为RE₂（HL）₂（H₂L）₂·phen·nH₂O，探讨了配合物的成键特点及光谱性质。测定了4个配合物的晶体结构，X-单晶衍射结果表明，配合物[RE（H₂L）（HL）（H₂O）₃]₂·phen·4H₂O（RE=Sm、Eu、Gd）的每个单元均为两个结构相似的9配位配合物，每个配合物中有两个2-羰基丙酸水杨酰腙和三个水分子参与了配位，同时还有一个1，10-菲啰啉分子和四个水分子游离于晶格中，形成了三维网状的超分子化合物。镝配合物[Dy（HL）（phen）（NO₃）（H₂O）₂]·H₂O的晶体则有所不同，它是由2-羰基丙酸水杨酰腙、1，10-菲啰啉、硝酸根和两个水分子构成的9配位配合物，晶格中还存在一个游离的水分子。配合物在空间均呈扭曲的单帽四方反棱柱。 通过TG—DTG—DSC热分析研究了配合物RE₂（HL）₂（H₂L）₂·phen·nH₂O在4个升温速率下的热分解过程，利用Kissinger法和Ozawa法计算了各配合物主要分解阶段的表观活化能。对晶体[Eu（HL）（H₂L）（H₂O）₃]₂·phen·4H₂O在4个升温速率下的三个热分解阶段，分别采用三种积分法和两种微分法对非等温动力学数据进行了线性回归处理，得到了三个不同阶段的动力学方程、分解机理及动力学参数。 选取6个具代表性的稀土与2-羰基丙酸水杨酰腙、1，10-菲啰啉配合物，采用生长速率法和孢子萌发法对番茄灰霉病菌、烟草赤星病菌和小麦条锈病菌等3种菌进行了生物活性试验。结果表明，6种配合物均具有一定的抑菌活性，其中Y（H₂L）₃（H₃L）·5H₂O、Dy₂（H₂L）₂（HL）₂（phen）·2H₂O两种配合物的抑菌效果较为明显，在40ug·ml^-1时Y（H₂L）₃（H₃L）·5H₂O对番茄灰霉病菌抑菌率为100％，在80ug·ml^-1时对烟草赤星病菌的的抑菌率为100％，而Dy₂（H₂L）₂（HL）₂（phen）·2H₂O在0.05ug·ml^-1时对小麦条锈病菌孢子萌发的抑制率仍高达79.7％。更多还原

【Abstract】 In mixed solution of aqua-ethanon, novel twelve rare earth (RE= La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu and Y) complexes with 2-oxo-propionic acid salicyloyl hydrazone(C10H10N2O4, H3L) and 1,10-phenanthroline(C12H8N2, phen) had been synthesized. The formulae RE2(HL)2(H2L)2.phen.nH2O were determined by elemental analysis, IR, UV, FS, 1H NMR and thermoanalysis. The bonding character and spectra properties were discussed. The crystals of four complexes (RE= Sm, Eu, Gd, Dy) were obtained and determined by X-ray single crystal diffraction. There were two similar 9-coordinated complexes in every crystal unit of [RE(HL)(H2L)(H2O)3]2.phen.4H2O (RE=Sm, Eu, Gd), in which RE(III) were coordinated by two tridentate H3L ligands and three water molecules. There were a free 1,10-phenanthroline and four water in the crystal cell. The complex formed a three-dimensional network supramolecular. For [Dy(HL)(phen)(NO3)(H2O)2].H2O monocrystal, the Dy atom was nine-coordinated by linking to one tridentate H3L ligand, one bidentate phen, one bidentate nitrate and two water molecule. The coordination polyhedron around RE(III) (RE= Sm, Eu, Gd, Dy) was a distorted monocapped square antiprism.The thermal decompositions of the complexes RE2(HL)2(H2L)2.phen.nH2O were carried out by TG-DTG-DSC curve. The Kissinger’s method and Ozawa’s method were used to calculate the activation energy value of two main decomposition stages. For [Eu(HL)(H2L)(H2O)3]2.phen.4H2O crystal, the non-isothermal kinetic data of three stages of the decompositions were analyzed by three integral methods and two differential methods. The most probable reaction mechanism and the kinetic equation were investigated by comparing the kinetic parameters.The biologic activity of six complexes for three bacteria: Botrytis cirerea Pers.ex Tris., Alternaria alternata (Fries) keissler and wheat rust were carried out by growth rate method and spore sprout method. The result showed that all six complexes possessed acertain bacteriostasis activity. It is obvious that Y(H2L)3(H3L).5H2O, Dy2(H2L)2(HL)2(phen).2H2O had good antimicrobial activities. The inhibitory rate of Y(H2L)3(H3L).5H2O for Botrytis cirerea Pers.ex Tris. is 100% at 80ug.ml-1, for Alternaria alternate (Fries) keissler is 100% at 40ug.m-1, and that of Dy2(H2L)2(HL)2(phen).2H2O for spore growth of wheat rust is still high of 79.7% at 0.05ug.ml-1.Yang Rui (Chemistry) Directed by He Shuiyang and Wen Zhenyi更多还原