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

为了获得具有增塑剂可变离子载体等新功能的离子识别主体分子，以12-冠-4（12 cw 4）、15-冠-5（15 cw 5）和18-冠-5（18 cw 6）为离子识别单元，考察了偶联邻苯二甲酸和杯[4]芳烃作为间隔单元的方法。合成了邻苯二甲酸酯型均相双冠醚（12 cw 4）、双冠醚（15 cw 5）、双冠醚（18 cw 6）：A>和异相双冠醚（12 cw 4）-（15 cw 5）、（15 cw 5）-（18 cw 6）、（12 cw 4）-（18 cw 6）：B>和杯[4]芳烃型均相双（冠）醚双（12 cw 4）、双（15 cw 5）、双（18 cw 6）：C>的电化学性能进行了表征，通过比较聚以双冠醚为基体的PVC膜电极的基本性能和离子选择性由高到低的顺序为双（12 cw 4）>双（15 cw 5）>双（18 cw 6），虽然双（12 cw 4）证明了Na^+离子的选择性， ...更多信息 与市售Na^+离子载体相似。另一方面，证明了B型的（15 cw 5）-（18 cw 6）具有增塑剂变体类型的新功能性质，即通过使用增塑剂的种类，对不同的离子会出现如下选择性。例如，在（15 cw 5）-（18 cw 6）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）、癸二酸二（2-乙基己基）酯（DOS）和二苄基醚（DBE）体系以及乙酸苄酯（BA）体系电极分别显示出对K^+离子、Rb^+离子和Cs^+离子的选择性。C型衍生物还具有增塑剂变体的性质。特别是在双（15-冠-5）基电极中，DOP体系电极对Ag^+离子具有选择性（- log k <pot>^&lt;Ag，K&gt; = 1.4），而NPOE体系电极对K^+离子具有选择性（- log k <pot>^&lt;K，Ag&gt; = 1.5）。具有增塑剂等功能的新型离子载体的变异性，由于被认为依赖于离子捕获位点的灵活性，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（23种）的Ag^+离子载体的功能表达式。少

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