| Co-Investigator(Kenkyū-buntansha) |
FUJIMORI Keiichi Osaka Institute of Technology, Faculty of Engineering, Lecturer, 工学部, 講師 (70319573)
MORIUCHI Takayo (KAWAKAMI Takayo) Osaka Institute of Technology, Faculty of Engineering, Assistant Professor, 工学部, 助教授 (60288751)
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| Research Abstract |
To obtain an ion discriminative host molecule with the new function such as plasticizer variable ionophore, 12-crown-4(12cw4), 15-crown-5(15cw5) and 18-crown-5(18cw6) were adopted as the ion recognition division, and the methods for coupling to phthalic acid and calix[4]arene as the spacer division were examined. The resulting 9 kinds of derivatives, phthalic ester type homogeneous bis(crown )s <bis(12cw4), bis(15cw5), bis(18cw6): A> and heterogeneous bis(crown)s <(12cw4)-(15cw5), (15cw5)-(18cw6), (12cw4)-(18cw6): B> and calix[4]arene type homogeneous bis(crown)s <bis(12cw4), bis(15cw5), bis(18cw6): C> were characterized by electrochemical measurement to estimate by comparison of electrochemical properties of poly(vinylchloride)(PVC) membrane electrodes based on bis(crown)s.
Fundamental property and ion selectivity of the electrode based on A-type derivatives decreased in order of bis(12cw4)>bis(15cw5)>bis(18cw6), though bis(12cw4) demonstrated the Na^+ ion selectivity which is comparab
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le to the commercial Na^+ ionophore. On the other hand, it was proved that (15cw5)-(18cw6) of B-type has the new functional property of the plasticizer variation type that is the selectivity will appear for different ion by the kind of using plasticizer as following. For example, in the (15cw5)-(18cw6) based electrodes, 2-fluorophenyl-2-nitrophenyl ether(FNDPE) and o-nitrophenyl octyl ether(NPOE)-system, di-n-octylphthalate(DOP), bis(2-ethylhexyl)sebacate(DOS) and dibenzyl ether(DBE)-system and benzyl acetate(BA)-system electrodes shows the selectivity for K^+ ion, Rb^+ ion, and Cs^+ ion, respectively. The C-type derivatives also have the property of the plasticizer variation. Especially, in the electrode based on bis(15-crown-5), DOP system electrode shows Ag^+ ion selectivity(- log k^<pot>_<Ag,K> = 1.4), while NPOE system one shows K^+ ion selectivity (- log k^<pot>_<K,Ag> = 1.5). The new ionophore possessing function such as plasticizer variation property, because it is considered depend on the flexibility of ion capture site, it was judged that the heavy metal ion discrimination is also possible by the entropy effect, and it was made to develop to the functional expression as Ag^+ ionophore of Schiff base (23 kinds). Less
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