Selective Ion Separation Based on the Interaction between Ion and Electron Transfer Reactions at Liquid/Liquid or Liquid/Membrane Interface.

在水(W) /有机（Org）溶液或W/膜(M)界面上的离子转移由两相之间的Galvani电位差（DELTApsi）控制。本研究的目的是开发一种高灵敏度离子分离方法，该方法利用氧化还原（电子转移）反应严格控制DELTA psi的界面。结果总结如下。采用液/液界面电荷转移伏安法（VCTLLI）研究了含铁氰化物、亚铁氰化物、氢氧化物离子或对苯二酚等的W与含二茂铁、四噻吩、四氰喹二甲烷等的Org在界面处的电子转移反应，并推导了电子转移的理论方程。电子转移由两相中氧化还原物质的标准氧化还原电位、浓度、扩散系数和活性决定。结合电子转移方程和离子转移方程，提出了离子与电子转移反应相互作用的理论，并进行了实验验证。温度对离子转移的影响主要归因于溶剂性质随温度的变化，共存盐的转移可以从水活度的变化和W中离子对的形成随盐浓度的变化来解释。这些效应有望非常有效地实现由电子转移控制的离子的高度选择性分离。伴随离子转移的DELATpsi振荡不仅影响离子的分离，而且与生物体的激发有着深刻的关系。基于VCTLLI对离子转移和离子对在界面上的吸附的研究，并考虑了两相的离子平衡，提出了振荡过程的第一个定量解释。少

The ion transfer at an interface of aqueous (W) /Organic (Org) solution or W/Membrane (M) is controlled by the Galvani potential difference (DELTApsi) between the two phases. The objective of the present work was to develop a methodology for the highly sensitive ion separation utilizing the interface of which DELTA psi is controlled critically by the redox (electron transfer) reaction. The results are summarized in the following.The electron transfer reactions at the interface between W containing ferricyanide, ferrocyanide, hydroxide ions or hydroquinone, etc. and Org containing ferrocene, tetrathiafulvalene, tetracyanoquinodimethane, etc. were investigated by the Voltammetry for the Charge Transfer at the Liquid/Liquid Interface (VCTLLI), and theoretical equations for the electron transfer were derived. The electron transfer is determined by the standard redox potential, concentration, diffusion coefficient, and activity of the redox species in both the phases. Combining the equation … More s for the electron transfer and those for the ion transfer, a theory for the interaction between ion and electron transfer reactions was proposed, and the theory was confirmed experimentally.The effect of temperature on the ion transfer is mainly ascribable to the change in properties of solvents with the temperature, and that of coexisting salts is explained from both variations of water activity and the ion-pair formation in W with the salt concentrations. These effects are expected to be very effective to realize a highly selective separation of ions controlled by the electron transfer.The oscillation of DELATpsi accompanied with the ion transfer not only influences the separation of ions but also relates profoundly to the excitation of living organisms. The first quantitative explanation on the process of the oscillation was proposed based on the investigation on the ion transfer and adsorption of ion-pair at the interface by VCTLLI and the consideration of the ionic equilibrium in both the phases. Less