Studies for High performance and Practical Use of Neutral Carrier-Type Ion Sensors Based on Silicone-Rubber Membranes

本论文的目的是研究基于硅橡胶膜和溶胶-凝胶膜的中性载体型离子传感器的高性能和实用化。本文研究的离子传感器是离子敏感场效应晶体管（ISFET）和离子选择性电极（伊势）。杯[4]芳烃离子载体主要用作钠中性载体。主要研究结果如下：1）杯[4]芳烃离子载体的结构不对称性和寡聚化2）通过共价键将钠中性载体如杯[4]芳烃离子载体成功地固定到硅橡胶膜上，以获得高度耐用，用于离子电极的生物相容性中性载体基传感膜。合成了杯芳烃结构的二甲基硅氧烷衍生物，以解决杯芳烃结构改性硅橡胶膜的一些缺点。包封常规中性载体如缬氨霉素和双（12-冠-4）的化学修饰，使其成为有机-无机杂化离子敏感膜。6）本文研究的中性载体型钠离子传感器在传感器性能、耐久性和生物相容性方面均表现出较高的性能。并成功地应用于血清、尿等体液中钠的测定。

The aim of this work is to study for high performance and practical use of neutral-carrier-type ion sensors based on silicone-rubber membrane and sol-gel-derived membranes. The ion sensors studied here were ion-sensitive field-effect transistors (ISFET) and ion-selective electrodes (ISE). Calix [4] arene ionophores were mainly employed here as the sodium neutral carriers. The research results are as follows.1) Calix [4] arene ionophores incorporating structural unsymmetry and oligo (siloxane) group have been designed to obtain highly dispersible calixarene ionophore in silicone rubber.2) Sodium neutral carriers such as calix [4] arene ionophores have been successfully immobilized to silicone rubber membranes by covalent bonding, in order to attain highly durable, biocompatible neutral-carrier-based sensing membranes for ion-selectrodes.3) Oligo (dimethylsiloxane) derivatives carrying calixarene moiety have been synthesized to alleviate some drawbacks for the silicone-rubber membranes modified chemically with calixarene moiety.4) Sol-gel-derived membranes encapsulating a conventional neutral carrier such as valinomycin and bis (12-crown-4) have been designed as organic-inorganic hybrid ion-sensing membranes.5) Chemical modification of sol-gel-derived membranes with alkoxysilylated neutral carriers were attrmpted aiming at modification of glass membranes with neutral carriers.6) Any of the neutral carrier-type sodium ion sensors studied here showed high performance in sensor property, durability, and biocompatibility. Also, they have been sucessfully applied to sodium assay in human body fluid as sera and urine.