Development of Electrochemical Sensor System for in situ Detection of NO in Living Body

本研究的目的是研制一种高选择性、高灵敏度的活体NO原位电化学传感器系统。主要研究结果如下：（1）成功制备了不同孔径比的活性炭纤维等多种微电极材料。(2)An用Nafion、α-环糊精和聚二烯丙基二甲基氯化铵组成的三层膜覆盖的电极对NO具有稳定的氧化电流，对NO具有高的选择性和灵敏度。在电极上的Nafion膜中加入α-FeOOH，可以使NO在电极表面附近富集，导致NO氧化电流的增加，敏感性（三宅）。(3)An研究了用含有各种金属卟啉的三层膜覆盖的电极性能。其中，Fe（III）（TPFPPCl）表现出最高的催化活性，并且其催化机理被阐明（Ikeda）。(4)To通过NO的包结效应提高灵敏度和选择性，合成了各种杯芳烃衍生物。具有磺酸官能团的衍生物显示出良好的性能（Kimura）。(5)NO在覆盖有Nafion和聚（二烯丙基二甲基氯化铵）的电极上以高灵敏度检测从培养的牛肺动脉内皮细胞释放的。通过分别添加乙酰氯和L-NAME观察到NO氧化电流的增加和减少（Yamatodani）。

Purpose of the present study is development of in situ electrochemical sensor system to detect NO in living body with high selectivity and sensitivity. The following results are obtained :(1)Various carbon materials to be used as micro-electrode were successfully prepared, such as activated carbon fibers with various pore ratios(Yamaguchi). (2)An electrode covered with three-layered films consisting of Nafion, α-cyclodextrin, and poly(diallyldimethyl ammnonium chloride)gave stable NO oxidation current with high selectivity and sensitivity to NO.Addition of α-FeOOH in Nafion film on an electrode, which is known to adsorb NO selectively, concentrated NO near electrode surface, resulting in an increase in amount of NO oxidation current, i.e., sensitivity(Miyake). (3)An electrode performance covered with three-layered films containing various metal porfirin was investigated. Among them, Fe(III)(TPFPPCl)showed the highest catalytic activity and its catalytic mechanism was clarified(Ikeda). (4)To increase in sensitivity and selectivity by inclusion effects of NO, various calixarene derivatives are synthesized. A derivative with sulfonic acid functional group showed good performance(Kimura). (5)NO released from cultured bovine pulmonary arterial endothelial cells was detected with high sensitivity over an electrode covered with Nafiohn and poly(diallyldimethyl ammnonium chloride). An increase and a decrease in NO oxidation currents were observed by the addition of acetylchorine and L-NAME, respectively, (Yamatodani).