【作者】 王建；

【导师】 陆路德；

【作者基本信息】 南京理工大学 ， 化学工程与技术， 2009， 博士

【摘要】 本文以L-色氨酸配体为基础,合成了系列Fe（Ⅱ）、Co（Ⅱ）、Ni（Ⅱ）、Zn（Ⅱ）、Cd（Ⅱ）和Mn（Ⅱ）的配位聚合物,对产物进行了谱学表征。通过X-射线衍射解析了六种化合物的单晶结构,研究了它们的热稳定性和Fe（Ⅱ）、Co（Ⅱ）、Ni（Ⅱ）和Mn（Ⅱ）配位聚合物的电化学性质。通过流动电位法对水溶液体系中氨基酸、二元羧酸和配合物结晶过程的研究,有助于进一步研究氨基酸配合物结晶和沉淀过程相界面的动电现象。全文的主要内容如下:由摩尔盐和L-色氨酸,通过水热法制备新型Fe（Ⅱ）-DL-trp混配型配位聚合物。进行元素分析、差热-热重分析、红外和紫外光谱、单晶X-衍射等的表征及循环伏安研究。该化合物属单斜晶系P2₁/c,具有中心对称空间群,为二维双链层状结构。每个亚铁离子Fe²⁺与一对外消旋体配合,形成内消旋化合物。由水合高氯酸钴（Ⅱ）和L-色氨酸通过水热法制备Co（Ⅱ）-DL-trp混配型配位聚合物,进行元素分析和差热-热重分析、红外和紫外光谱、单晶X-衍射等的表征及循环伏安研究。该化合物属单斜晶系P2₁/c,具有中心对称空间群,为无限二维层状结构。每个亚钴离子Co²⁺与一对色氨酸外消旋体配合,形成内消旋化合物。由水合高氯酸镍（Ⅱ）和L-色氨酸通过甲醇-水混合溶剂热法制备Ni（Ⅱ）-DL-trp混配型配位聚合物,进行元素分析和差热-热重分析、红外和紫外光谱、单晶X-衍射等的表征及循环伏安研究。该化合物属单斜晶系P2₁/c,每个镍（Ⅱ）原子位于反演中心,分别与1个L-trp分子和1个D-trp分子的氨基氮原子及羧基上1个氧原子,另1个L-trp分子和另1个D-trp分子羧基上各1个氧原子配位。每个L-trp和D-trp配体通过羧基与镍（Ⅱ）原子桥连,形成平行于bc平面方向的二维双链层状结构。由水合高氯酸锌（Ⅱ）和L-色氨酸通过甲醇-水混合溶剂热法制备Zn（Ⅱ）-DL-trp混配型配位聚合物,进行元素分析和差热-热重分析、红外和紫外光谱、核磁、单晶X-衍射等的表征。该化合物属单斜晶系C2/m,具有中心对称空间群。每个锌离子Zn²⁺与一对外消旋体配合,而形成内消旋化合物。由水合醋酸镉（Ⅱ）和L-色氨酸通过有机溶剂热法制备Cd（Ⅱ）-DL-trp混配型配位聚合物,进行元素分析和差热-热重分析、红外和紫外光谱及单晶X-衍射等的表征。该化合物属单斜晶系P2₁/c,具有中心对称空间群,为无限二维层状结构。每个Cd²⁺离子与一对色氨酸外消旋体配合,而形成内消旋化合物。由水合高氯酸锰（Ⅱ）和L-色氨酸通过水热法制备Mn（Ⅱ）-DL-trp混配型配位聚合物,进行元素分析和差热-热重分析、红外和紫外光谱、单晶X-衍射等的表征及循环伏安研究。该化合物属单斜晶系P2₁/c,具有中心对称空间群,为无限二维层状结构。每个Mn²⁺与一对色氨酸外消旋体配合,而形成内消旋化合物。运用流动电位法动态测定乙二酸、丁二酸和己二酸等含偶数碳原子的二元羧酸在不同温度下饱和溶液降温结晶过程的动电现象。当温度降至晶核出现时,流动电位值达到最低。此后当温度继续下降时,产生的微晶不断成长,流动电位呈上升趋势。二元羧酸饱和溶液起始温度越高,流动电位最低点相对应的温度越高;二元羧酸碳原子数越少且溶解度越大,流动电位最低点相对应的温度也越高。以流动电位法研究甘氨酸、L-色氨酸和L-谷氨酸饱和水溶液降温结晶过程。考察溶液酸度和起始温度对结晶过程中流动电位ν-结晶器温度t曲线的影响。甘氨酸饱和溶液在较高起始温度30和35℃下成核能力较差,在较低起始温度20和25℃下成核能力较强。起始温度相同的ν-t曲线表明溶液pH=7.0、pH=5.0和pH=4.0的条件下成核作用明显,等电点附近成核能力较差。L-色氨酸饱和溶液在较高起始温度35℃下成核能力较差,在较低起始温度20℃下成核能力较强。起始温度相同的ν—t曲线表明pH＞6.0的条件下成核能力较差,易析出不定型固体。L-谷氨酸饱起始温度30℃以下具有成核能力,酸度在等电点（pH=3.15）附近的溶液成核能力较强,后者与其等电点时L-Glu溶解度最小,容易析出晶体有关。用流动电位法对K₃[Fe（CN）₆]和K₄[Fe（CN）₆]饱和溶液降温结晶过程进行表征。当温度降至晶核出现时,流动电位值达到最低。此后当温度继续下降时,流动电位呈上升趋势。配合物饱和溶液起始温度越高,流动电位最低点相对应的温度越高。降温结晶过程中K₃[Fe（CN）₆]流动电位的最低点温度低于K₄[Fe（CN）₆]流动电位最低点相对应的温度。更多还原

【Abstract】 On the basis of L-trp ligand,a series of Fe（Ⅱ）,Co（Ⅱ）,Ni（Ⅱ）,Zn（Ⅱ）,Cd（Ⅱ） and Mn（Ⅱ） coordination polymers were synthesized by a hydrothermal or a mixed solvent-thermal method.The products were characterized by spectroscopy.The single crystal structure of six coordination polymers have been resolved by X-ray diffraction.Their thermal stability were investigated.The electrochemical properties of Fe（Ⅱ）,Co（Ⅱ）,Ni（Ⅱ） and Mn（Ⅱ）-trp coordination polymers were researched.Through the study on the crystallization process of aqueous solution of amino acids,dicarboxylic acids and complexes by streaming potential method,that will helps to further study on the crystallization or the precipitation process of amino acid complexes and the electrical characteristics on the solid-liquid interface.The research and main conclusion of this dissertation is shown as follows:The coordination polymer of Fe（Ⅱ） and DL-trp was formed by a hydrothermal method involving Mohr’ salt and L-tryptophan.The product was characterized by elemental and thermal analysis,IR and UV spectra,cyclic vohammogram and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group P21/c.The structural analysis shows that the complex assumes a two-dimensional double chain layered structure.The coordination polymer of Co（Ⅱ） and DL-trp was prepared by a hydrothermal method from hexaaqua-cobaltous perchlorate and L-tryptophan,and was characterized by elemental and thermal analysis,IR and UV spectra,cyclic vohammogram and single-crystal X-ray diffraction. The compound（monoclinic space group P2₁/c） shows a two-dimensional double chain layered structure.The cyrstallized coordination polymer has a centrosymmetric space group. Each Co²⁺ coordinate with a pair of racemes,and the complex is a mesomer.The coordination polymer of Ni（Ⅱ） and DL-trp was formed by a mixed solvent-thermal method from hexaaquanickel（Ⅱ） perchlorate and L-tryptophan.It was characterized by elemental and thermal analysis,IR and UV spectra,cyclic vohammogram and single-crystal X-ray difffraction.The crystal belongs to the monoclinic system,space group P2₁/c.The Ni（Ⅱ） atom is located on an inversion center and has an octahedral coordination geometry formed by four O atoms and two N atoms from D- and L-tryptophan ligands.Each D- and L-tryptophan ligand bridges the Ni（Ⅱ） atoms through the carboxylate group,leading to a two-dimensional structure parallel to the bc plane.The coordination polymer of Zn（Ⅱ） and DL-trp was prepared by a mixed solvent-thermal method and characterized by elemental and thermal analysis,IR,UV and ¹HNMR spectra,and single-crystal X-ray diffraction.The compound（monoclinic space group,C2/m） shows a two-dimensional double chain structure.The cyrstallized coordination polymer has a centrosymmetric space group.Each Zn²⁺ coordinate with a pair of racemes,and the complex is a mesomer.The coordination polymer of Cd（Ⅱ） and DL-trp was successfully prepared by a solvent-thermal method.It was characterized by elemental and thermal analysis,IR and UV spectra,and single-crystal X-ray diffraction.The compound（monoclinic space group P2₁/c） shows a two-dimensional double chain layered structure.The cyrstallized coordination polymer has a centrosymmetric space group.Each Cd²⁺ coordinate with a pair of racemes, and the complex is a mesomer.The coordination polymer of Mn（Ⅱ） and DL-trp was prepared by a hydrothermal method and characterized by elemental and thermal analysis,IR and UV spectra,cyclic vohammogram and single-crystal X-ray diffraction.The compound（monoclinic space group P2₁/c） shows a two-dimensional double chain layered structure.The cyrstallized coordination polymer has a centrosymmetric space group.Each Mn²⁺ coordinate with a pair of racemes, and the complex is a mesomer.The streaming potential of saturated solution of binary carboxylic acids,which have even carbon atoms,was determined to characterize crystallization under different temperatures.When the temperature was declined to the point where a crystal nucleus appeared,the streaming potential reached the minimum.Thereafter,as the temperature was sequentially lowered,some minicrystals grew,and the streaming potential presented an ascendant tendency.The higher the starting temperature of the acids saturated solution,the higher is the temperature corresponding to the streaming potential minimum.The less the carbon atoms in the acids and the greater the solubility of the acids are,the higher is the temperature of the streaming potential minimum.The streaming potential of saturated solution of Gly,L-Trp and L-GIu were determined to characterize crystallization in cooling process.The influence of solution acidity and the initial temperature to the v-t curve were investigated.The glycine solution has more competitive nucleating ability in higher initial temperature as 30 and 35℃,and less competitive nucleating ability in lower initial temperature as 20 and 25℃.It is shown to the v -t curve of the same initial temperature for the solution of pH=7.0,pH=5.0 and pH=4.0 have more evidently competitive nucleating ability.There is less competitive nucleating ability at isoelectric point.The L-Trp solution has more competitive nucleating ability in lower initial temperature as 20℃,and less competitive nucleating ability in higher initial temperature as 35℃.It is shown to the v-t curve of the same initial temperature for the solution of pH>6.0 have more evidently competitive nucleating ability.There is less competitive nucleating ability at isoelectric point.The L-Glu solution has more competitive nucleating ability below initial temperature 30℃and at isoelectric point（pH=3.15 ）.The latter is relevants to the solubility of L-Glu which is smallest at the pH value of isoelectric point and can easily deposit crystalThe streaming potential of saturated solution of K₃[Fe（CN）₆]and K₄[Fe（CN）₆]was determined to characterize crystallization under declining temperature process.When the temperature dropped to the point where crystal nucleus appeared,the streaming potential reached the minimum.Thereafter,the streaming potential presented an ascendant tendency. The higher starting temperature of the complex saturated solution is,the higher temperature corresponding to the value of streaming potential minimum is.The temperature of streaming potential minimum in K₃[Fe（CN）₆]supersaturated solution is lower than that in K₄[Fe（CN）₆] supersaturated solution.更多还原