Development of Capillary Electriphoretic Reactor and Its Application to Kinetically High-Peformance Metal Complexes

研制了毛细管电泳法(CER)。CER的基本思想是将CE的分离过程看作是金属络合物的化学反应。用CER方法研究了稀土(III)多氨基羧酸盐配合物和四齿氰基甲醛配合物与锌(II)、锰(II)的解离动力学。一般认为，稀土离子、锌(II)和锰(II)等金属离子的络合物是不稳定的，因为配位水分子在金属离子上的取代速率常数很大。相反，在毛细管前衍生化毛细管电泳法检测体系中，发现这些络合物是惰性的，不需要在载体缓冲溶液中添加配体。探索了新的动力学高效金属络合物。以硫杂杯[4]芳基四磺酸(TCAS)和2-(2‘-Hydroxyphenyl)-10-hydroxybenzo[h]quinoline(HPHBQ)为柱前络合剂，建立了柱前衍生化高效液相色谱系统测定超痕量镍(II)和铍(II)的方法。还证明了KD-HPLC法与TCAS和HPHBQ联用的实用性。

The capillary electrophoretic reactor (CER) has been developed. The basic idea of CER is to consider the separation process of CE as a chemical reactor for metal complexes. CER method was applied to investigate the dissociation kinetics of lanthanide (III) polyaminocarboxylate complexes and tetradentate cyanoformazane complexes with Zn(II) and Mn(II). In general, complexes of metal ions, such as lanthanide ions, Zn(II) and Mn(II), had been thought to be labile because of large substitution rate constants of coordinated water molecules at the metal ions. On the contrary, it was found that these camplexes had been inert to be amenable to the detection in pre-capillary derivatization CE system with no addition of the ligand in a carrier buffer solution.Inquires into new kinetically high-peformance metal complexes has been made. Thiacalix[4]arenetetrasulfonate (TCAS) and 2-(2'-Hydroxyphenyl)-10-hydroxybenzo[h]quinoline (HPHBQ) were examined as a pre-column chelating reagent for the determination of ultra trace Ni(II) and Be(II) by KD-HPLC of the pre-column derivatization HPLC system with no addition of the ligand in an eluent, respectively. The practical applicability of KD-HPLC methods with TCAS and HPHBQ was also demonstrated.