Spectroscopic Investigation of Electrode Surfaces Prepared by Self-Assembling Method

1. 利用美国威斯康星大学麦迪逊分校的皮秒SHG系统和北海道大学的纳秒SHG系统，研究了金电极上的表面反应。对市售FTIR光谱仪进行了改进，以实现对电极表面化学物质的电位调制原位FTIR测量。结果表明，二茂铁部分被氧化/还原时，烷基链和二茂铁环的取向发生了变化。此外，由于电荷偶极相互作用，我们发现即使没有氧化还原基团的巯基烷腈单层的取向也会受到电极电位的影响。合成了以卟啉为光敏基团、奎宁为电子接力基团、硫醇为吸附基团的光致电转移单分子，并将其附着在金上。研究了膜的光响应特性。用电化学石英微天平（EQCM）监测巯基醌/对苯二酚单层/电解质界面上的传质。在低pH区没有检测到质量传递，而在高pH区，发现阳离子传递伴随着氧化还原反应。

1. SHG study of Au electrodeSurface reactions at Au electrode were investigated by using pico second SHG system in UW-Madison and nano second SHG system in Hokkaido University.2. In-situ FTIR stydy of potential dependent structure/orientation of self-assembled monolayer on goldCommercially available FTIR spectrometer was amended to perform potential modulated in-situ FTIR measurement of chemical species on electrode surface. It was found that orientation of alkylchain and ferrocene ring changed when the ferrocene moiety was oxidized/reduced. Furthermore, we found even the orientation of the monolayer of mercaptoalkanenitrile which has no redox group was affected by electrode potential due to charge-dipole interaction.3. Construction of a monolayer for photo-induced electro transferA molecule which contains porphyrine as photo-sensitive group, quinine as electron relay and thiol as adsorbing group was synthesized and was attached on gold. Photo-response of the monolayer was investigated.4. EQCM study of transport at mercapto-quinone/hydroquinone monolayer/electrolyte interfaceElectrochemical quartz microbalance(EQCM) was employed to monitor the mass transport at the above mentioned interface. In low pH region no mass transport was detected but at high pH region, cation transport was found to accompany the redox reaction.