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

水(W)/有机(Org)溶液或W/膜(M)界面上的离子迁移受两相之间的电流电位差(DELTApsi)控制。本工作的目的是开发一种用于高灵敏离子分离的方法，该方法利用界面上的Delta psi受到氧化还原(电子转移)反应的关键控制。用液/液界面电荷转移伏安法(VCTLLI)研究了含W的铁氰化物、亚铁氰化物、氢氧离子或对苯二酚等与含二茂铁、四硫富瓦烯、四氰基喹甲烷等有机化合物之间的界面电子转移反应，推导了电子转移的理论方程。电子转移由标准氧化还原电势、浓度、扩散系数和氧化还原物种在两相中的活性决定。组合方程…在S关于电子转移和离子转移的基础上，提出了离子和电子转移反应的相互作用理论，并从实验上证实了该理论.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，共存盐的影响可从水的活度和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高选择性离子分离。伴随着离子转移的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对离子对在界面上的迁移和吸附的研究，以及对两相离子平衡的考虑，首次对振荡过程进行了定量解释。较少

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