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

本研究研究了铬（III）或钴（III）离子合成三型氨基酸配合物的立体选择性、固溶异构化行为、液相色谱（LC）和电化学行为。首先，讨论了氨基酸配体的双链与配位结构对氢键能力的影响。获得了铬（III）配合物光化学外消旋和配体交换反应的新结果。同时，基于钴（III）氨基酸配合物的氢键能力，也进行了固定相或电离层的开发，得到了以下结果：(1)建立了含谷氨酸配体和不含谷氨酸配体的cob - alt（III）配合物立体选择性合成的常规方法，以及各异构体的分离分析方法；(2)制备了配合物修饰的固定相，利用配合物上的游离羧基与氨基丙基键合硅胶结合；(3)制备配合物直接吸附于硅胶表面的LC柱；将继续使用在案例(2)或案例(3)上制备的新LC柱进一步研究各种物质的洗脱行为。同时，还将尝试制备含有乙二胺或草酸盐配体的离子配合物，以开发有用的传感器离子载体。

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.