Development of statinalry-phase and ionohore based on metal-aminoaciato complex with hydrogen-bonding ability

本论文研究了三型氨基酸与铬（III）、钴（III）离子配合物的立体选择性合成、固相和溶液异构化行为、液相色谱和电化学行为。首先，讨论了氨基酸配体的双链或配位结构对氢键结合能力的影响。对铬（Ⅲ）配合物的光化学消旋反应和配体交换反应进行了研究。同时，基于钴（III）氨基酸配合物的氢键作用，开发了固定相或离子载体，并取得了以下结果：（1）建立了含谷氨酸配体和不同配体的钴（III）配合物的立体选择性合成及各异构体分离分析的常规方法;（2）利用络合物上的羧基与氨丙基键合的硅胶键合，制备了络合物修饰的固定相，（3）制备了络合物直接吸附在硅胶表面的液相色谱柱;将继续使用根据情况（2）或情况（3）制备的新LC柱对各种物质的洗脱行为进行进一步研究。此外，我们亦将尝试以乙二胺或草酸盐为配位体的离子型配合物的制备，以开发出可应用于感测器的离子载体。

In this research, the stereoselectivity on syntheses of tris-type aminoacidato complexes with chromiuxn(III) or cobalt(III) ion, their isomerization behavior at solid-state and solution-state, liquid-chromatography (LC) and electrochemical behavior had been studied. Above all, the differences of hydrogen-bonding ability based on Bide-chain of aminoacidato ligands or coordination structure were discussed. Interesting results for the photochemical racemization and ligand-exchange reaction of chromium(III) complexes were obtained, newly. While, development of the stationary phase or ionophore based on the hydrogen-bonding ability of cobalt(III) aminoacidato complexes were also proceeded and the following results were obtained ;(1) routine methods were established in the stereoselective syntheses of cob alt(III) complexes containing both glutamate ligand and the different ones, and the separation and analytical methods for each isomers ;(2) stationary phase modified with complexes were prepared, which were bonded to aminopropyl-bonded silicagel by use of free carboxyl-group on complexes ;(3) LC column, where complexes were directly adsorbed at the surface of silicagel, was prepared ;Further study for the elution behavior of various substances with new LC columns prepared on case (2) or case (3) will be continued. And, Study on the preparation of ionic complexes containing ethylenediamine or oxalate ligand will be also attempted toward the development of useful ionophore for sensor.