DETECTION AND EVALUATION OF INTERACTION IN SOLUTION WITH SECONDARY EQUILIBRIUM LIQUID CHROMATOGRAPHY

本研究取得的主要成果如下：1.将离子分配到带相反电荷的离子胶束中可以通过静电模型或方便地通过离子交换模型来描述。过渡金属阳离子在阴离子胶束中的分配可以例如由涉及抗衡离子和配体的浓度的模型表示。二级平衡液相色谱研究表明，胶束和溶液之间的界面处的金属离子的络合作用受到胶束的表面电荷的抑制。该方法还允许评价胶束的解离，当应用于阴离子与阳离子胶束的分离时。二级平衡色谱法测定了冠醚与某些硬阳离子的络合常数。我没有发现溶液相和离子交换树脂相的络合作用有明显的差别。利用这一事实，建立了一种新的冠醚分离方法，并优化了实验条件，精确测定了络合常数.研究发现，聚氧乙烯分子的构象变化影响着聚氧乙烯分子的分配。稳定构象（螺旋形和锯齿形）之间的能量差已通过分子力学计算。所得结果与聚氧乙烯的保留模型有关。基于该模型的分析很好地解释了保留行为。

Results obtained in the present research can be summarized as follows :1. The partition of ions into an oppositely charged ionic micelle can be described by an electrostatic model or conveniently by an ion-exchange model. The partition of transition metal cations into an anionic micelles can be for example represented by the model involving the concentrations of a counter ion and a ligand. Secondary equilibrium liquid chromatographic investigation has indicated that the complexation of a metal ion at the interface between micelles and solution is suppressed by the surface charges of the micelles. This method has also permitted the evaluation of the dissociation of a micelle, when applied to the separation of anions with a cationic micelle.2. Secondary equilibrium chromatography has allowed us to determine the complexation constants of crown-ethers with some hard cations. I have not found no marked difference in the complexation between in solution phase and in the ion-exchange resin phase. This fact has been utilized to develop a novel separation method of crown-ethers and to optimize the experimental condition for precise determination of the complexation constants.3. It has been found that the partition of polyoxyethylenes is affected by the conformational changes of polyoxyethylenes. Differences in energy between stable conformers (helix and zigzag form) have been calculated by molecular mechanics. The results have been involved in a retention model of polyoxyethylenes. The analysis based on the developed model has well explained the retention behaviors.