Development of Ion Sensor Based on Ion Recognitiozable Host Compond, Calix-arene Linkaged Crown Unit

基于离子可识别主体化合物杯芳烃连接冠单元的离子传感器的研制

• 批准号: 12650800
• 负责人: SHIBUTANI Yasuhiko
• 金额: $ 2.56万
• 依托单位: Osaka Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650800/
• 关键词: Calix[4]arene type homogeneous bis(crown); Phtalate ester type heterogeneous bis(crown); Plasticizer variable ionophore; Sodium ion selective electrode; Silver ionophore; PVC membrane electrode; ナトリウムイオンセンサ; ビス(クラウン); 電位差測定法; ニュートラルキャリア; カリクスアレン

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 … More 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

为了获得具有增塑剂可变离子载体等新功能的离子鉴别宿主分子，采用12-冠-4（12cw4）、15-冠-5（15cw5）和18-冠-5（18cw6）作为离子识别分裂，并研究了偶联邻苯二甲酸和杯芳烃作为间隔分裂的方法。通过电化学测量对得到的9种衍生物进行了表征，分别为邻苯二甲酸酯型均相的bis(crown)s <bis（12cw4）、bis（15cw5）、bis（18cw5）、bis(18cw6): A>和非均相的bis(crown)s <(12cw4)-(15cw5)、bis(12cw4) -(18cw6): B>和杯状[4]芳烃型均相的bis(crown)s <bis（12cw4）、bis（15cw5）、bis(18cw6): C>，并比较了基于bis(crown)s的聚氯乙烯（PVC）膜电极的电化学性能。基于a型衍生物的电极的基本性质和离子选择性依次为bis(12cw4)>bis(15cw5)>bis(18cw6)，尽管bis（12cw4）表现出与商用Na^+离子载体相当的Na^+离子选择性。另一方面，证明了b型增塑剂(15cw5)-(18cw6)具有增塑剂变异型的新功能性质，即增塑剂的使用种类对不同离子的选择性表现如下。例如，在(15cw5)-(18cw6)基电极中，2-氟苯基-2-硝基苯基醚（FNDPE）和邻硝基苯基辛基醚（NPOE）体系、邻苯二甲酸二辛酯（DOP）、二（2-乙基己基）癸二酸酯（DOS）和二苄基醚（DBE）体系和乙酸苄酯（BA）体系电极分别对K^+离子、Rb^+离子和Cs^+离子表现出选择性。c型衍生物还具有增塑剂变异的性质。特别是在基于bis（15-冠-5）的电极中，DOP体系电极具有Ag^+离子选择性（- log k^<锅>_<Ag, k > = 1.4），而NPOE体系电极具有k^ +离子选择性（- log k^<锅>_< k,Ag> = 1.5）。新型离子载体具有增增剂变化特性等功能，由于考虑到它依赖于离子捕获位点的柔韧性，因此通过熵效应判断重金属离子的识别也是可能的，并将其发展为席夫碱Ag^+离子载体（23种）的功能表达。少

项目成果

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安田洋一郎, 森内隆代, 澁谷康彦: "電位差測定法による新規カリクスアレン型ピス(12-クラウン-4)のアルカリ金属イオン識別能の評価"Review of Polarography. 47・3. 160-160 (2001)

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Ueda Masato, Akiyo Komai, Keiichi Fujimori, Takayo Moriuchi-Kawakami, Yasuhiko Shibutani: "Evaluation of a dioxime-type Schiff base-poly(vinyl chloride) membrane as a silver-ion selective electrode"The Japan Society for Analytical Chemistry. 51, 9. 779-78

Ueda Masato、Akiyo Komai、Keiichi Fujimori、Takayo Moriuchi-Kawakami、Yasuhiko Shibutani：“二肟型席夫碱聚氯乙烯膜作为银离子选择性电极的评估”日本分析化学学会。