Analysis of the mechanism of charge-transfer coupling in nanometer-scale liquidliquid wo-phase systems and its application to separation science

我们研究了纳米级液-液两相体系中的电荷转移耦合，重点研究了纳米级液-液两相系统中电荷转移耦合的基本性质，并构建了代表纳米级液-液系统电荷转移耦合的各种体系。此外，基于我们在这些体系中发现的新发现、新现象和新规律，我们开展了界面电化学不稳定性的研究。首先，我们提出了在金表面的硫醇衍生物自组装单分子膜上涂覆一层疏水离子液体来表征电荷转移耦合的基本性质的体系，并阐明了这类体系的电化学性质。其次，我们从四个不同方面研究了微液-液体系中的电荷转移过程：i)。离子液体乳状液相边界电位法的机理，II)e-…速率的测定利用离子转移和电子转移的耦合，在微管顶端的微液-液界面上形成更多的电子转移，iii)反胶束中荧光探针周围的溶剂化动力学，以及iv)大的单层囊泡的跨膜电荷转移。我们证明了电化学不稳定性实际上是界面的热力学不稳定性，并通过证明这种不稳定性存在于许多不同的体系中来论证了这一新概念的普遍性。我们在进行这个项目中取得的另一个重要进展是开辟了一个新的电化学分支，表明疏水离子液体和水之间的新的液-液界面可以是非极化的，也可以是极化的，这取决于形成离子液体的离子的性质以及溶解在水中的离子的类型。由疏水性离子液体制成的盐桥可以作为一种概念上依赖于相界势的新型盐桥，并可以取代百年来最常用的基于扩散势的传统盐桥。我们还研究了可用于构建用于研究受限空间中电荷转移耦合的纳米级结构控制系统的纳米级自组装单分子膜的基本性质，并获得了大量的科学和技术知识。较少

We studied the charge-transfer coupling in nanometer-scale liquid-liquid two-phase systems with emphasis on their fundamental properties and with construction of a variety of liquid-liquid systems that represent the salient features of charge-transfer coupling in nanometer-scale liquid-liquid systems. Furthermore, based on the new findings, phenomena, and laws we found in these systems, we developed the study of the electrochemical instability of interface. First, we proposed systems that represent the fundamental properties of the charge-transfer coupling, using a thin layer of hydrophobic ionic liquid coated on a self-assembled monolayer of a thiol-derivative on gold surface and clarified the electrochemical properties of such systems. Second, we studied the charge transfer processes in micro liquid-liquid systems from four different aspects : i). the mechanism of the way of determining the phase-boundary potential in emulsions of ionic liquids, ii) the determination of the rate of e … More lectron transfer at the micro liquid-liquid interface formed at the tip of a micropipette, making use of the coupling of ion transfer and electron transfer, iii) the solvation dynamics surrounding fluorescent probes in reverse micelles, and iv) the charge transfer across the membrane of a large unilamellar vesicle. We showed that the electrochemical instability is in fact a thermodynamic instability of the interface and demonstrated the generality of this new concept by showing that this instability exists in many different systems. Another important development we made in conducting this project is the opening of a new branch of electrochemistry by showing that a new liquid-liquid interface between a hydrophobic ionic liquid and water can be electrochemically either nonpolarized or polarized, depending on the nature of the ions forming the ionic liquid and also the type of ions dissolved in water. Salt bridges made of a hydrophobic ionic liquid can work as a conceptually new salt bridges relying on the phase-boundary potential and can substitute traditional salt bridges based on the diffusion potential that have been used most imperatively over one hundred years. We also studied the fundamental propertied of nanometer-scale well-defined self-assembled monolayers that can be useful in constructing nanometer-scale structure-controlled systems for studying charge-transfer coupling in confined space and garnered substantial scientific as well as technological knowledge on such systems. Less