Nano-Properties of Organized Monolayers and Their Control

对自组装的硫醇单体（SAMs）的表面酸/基属性的评估，对黄金已经使用表面质量倾斜方法来指导我们在这个项目中开发。“The Surface Mass titratioh”，在其中，Electrode表面due到离子关联的质量变化是测量了SAMs使用石英晶体微生物的质量，具有评估两者表面pKa和酸密度的能力。我们研究了单组分和混合SAMs对COOH-和NH 2终止SAMs表面pKa的链长度、电泳解决方案和表面酸密度的影响。它是由这些结果来证明的，即表面pKa依赖于SAM或其使用的酸/基中心的结构。这一依赖性的主要起源被包括在表面电荷物种之间形成的由酸/基equilibrium形成的深层再脉冲相互作用。我们还发现，表面pKa是可控制的：当应用时，pKa被转移到负方向。终端COOH和解决方案中的离子关联是在详细情况下进行的，以确定分级期间质量变化的起源。根据去配置的COOH终止硫醇的质量测量，我们将溶剂疗法与SAM的终止羧基有关。The solvation number is also determined for LiイD1+イエD1，イイD1+イエD1 and CsイD1+イエD1。

The evaluation of surface acid/base properties of self-assembled thiol monolayers (SAMs) on gold has been conducted using the surface mass titration method we have developed in this project. The surface mass titratioh, in which the mass change of the electrode surface due to ion association is measured during the titration of SAMs using a quartz crystal microbalance, has the capability of evaluating both the surface pKa and acid density of SAMs simultaneously. We have examined effects of chain length, electrolyte solutions and surface acid density in single component and mixed SAMs on the surface pKa of COOH- and NH2-terminated SAMs. It is demonstrated by these results that the surface pKa is dependent on the structure of SAM or how acid/base centers are distributed. The main origin of this dependence is concluded to be the lateral repulsive interaction between the surface charged species formed by acid/base equilibrium. We also found that the surface pKa is controllable by the electrode potentials: the pKa shifted to negative direction when negative potentials were applied. The ion association between terminal COOH and cation in solution was examined in detail in order to clarify the origin of mass change during the titration. Based on mass measurements of desorbed COOH-terminated thiol, we conclude that the solvated cation is associated with the terminal carboxylate of SAM. The solvation number is also determined for LiィイD1+ィエD1, KィイD1+ィエD1 and CsィイD1+ィエD1.