Electrochemical Regulation of the Dynamic Behavior of Mososcopic Molecular Assemblies at Solid-Liquid Interfaces

(1)研究了紫红素单层膜在金电极表面的动力学行为。研究发现，氧化还原电位受到反阴离子的进出和结合相互作用的强烈影响，并且单层会记住形成单层时存在的阴离子，尽管在电解质溶液中加入较软的阴离子会消除记忆。从电荷补偿和单层结构的角度论证了动态离子转移过程的意义。(2)发现水不溶性染料金丝桃素掺入阳离子人工脂膜后，在水介质中电极表面发生氧化还原反应。氧化还原电位可通过调节脂质结构来控制。(3)十八烷基罗丹明B产生两种类型的电反射响应，一种是氧化还原过程引起的法拉第响应，另一种是动态吸附-脱附过程引起的非法拉第响应。表面活性剂的加入使氧化还原反应的可逆性增强，同时使非法拉第过程湮灭。(4)详细研究了七烷基紫素在水平接触的HOPG电极上对气体/七烷基紫素水溶液界面的伏安峰值响应。长钉出现的条件被列了出来。发现尖峰响应是由气/液界面的吉布斯膜与Langmuir单层之间的一阶法拉第相变过程引起的。动力学受成核-生长-碰撞动力学控制。(5)采用电反射法研究了金纳米粒子在单层修饰金电极上的固定动力学过程。在表面等离子体吸收波长处，观察到金纳米粒子由于电势依赖的充放电过程所引起的电反射响应。

(1) The dynamic behavior of a viologen monolayer on a Au electrode surface was investigated. It was found that the redox potential is strongly affected by ingress-egress of the counter anion coupled with the binding interaction and that the monolayer memorizes the anion present when forming the monolayer, though the memory is erased by the addition of a softer anion in the electrolyte solution. Significance of the dynamic ion transfer process was demonstrated in the terms of not only charge compensation but also monolayer structure.(2) It was found that a water-insoluble dye, hypericin, undergoes redox reaction on an electrode surface in an aqueous medium when the dye is incorporated into a cationic artificial lipid film. The redox potential was found to be controllable by regulating the lipid structure.(3) Octadecylrhodamine B gave rise to two types of electroreflectance responses, faradaic response due to the redox process and non-faradaic one due to, for example, dynamic adsorption-desorption process. Addition of a surfactant made the redox reaction be more reversible while annihilating the non-faradaic processes.(4) The voltammetric spike response of heptylviologen at a HOPG electrode horizontally-touched to gas/heptylviologen aqueous solution interface was investigated in detail. The conditions of the appearance of the spike were listed up. It was found that the spike response is due to the first-order faradaic phase-transition process between a Gibbs film at a gas/solution interface and a Langmuir monolayer. The dynamics was governed by nucleation-growth-collision kinetics.(5) Dynaunic processes of Au nano-particles immobilized on a monolayer-modified Au electrode were studied using electroreflectance methods. An electroreflectance response due to potential-dependent charging-discharging process of the Au nano-particle was clearly observed at the wavelength of surface plasmon absorption.