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

采用12-冠-4(12cw4)、15-冠-5(15cw5)和18-冠-5(18cw6)作为离子识别基团，考察了与邻苯二甲酸和杯[4]芳烃偶联的方法，以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。合成了9种邻苯二甲酸酯型均相双(冠)S、双(12cw4)、双(15cw5)、双(18cw6)：A&gt和异相双(冠)S&lt；(12cw4)-(15cw5)-(18cw6)、(12cw4)-(18cw6)：B&gt；杯[4]芳烃类均相双(冠)S&lt；A-型衍生物电极的基本性能和离子选择性按bi(12cw4)&gt；bi(15cw5)&gt；bis(18cw6)的顺序递减，而bi(12cw4)表现出与…相当的Na~+离子选择性更多的是商业Na~+离子载体。另一方面，还证明了B型的(15cw5)-(18cw6)具有增塑剂变型的新的功能性质，即增塑剂的使用种类对不同的离子会出现选择性。例如，在(15cw5)-(18cw6)基电极中，2-氟苯基-2-硝基苯基苯醚(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)癸酸酯(DOS)和二苯甲醚(DBE)体系和乙酸苄酯(BA)体系分别对K^+离子、Rb^+离子和Cs^+离子具有选择性。C-型衍生物还具有增塑剂的可变性。尤其是在双(15-冠-5)基电极中，DOP体系电极表现出对Ag~+离子的选择性(-logk^&lt；pot&gt；_&lt；Ag，K&gt；=1.4)，而NPOE体系电极表现出K~+离子选择性(-logk^&lt；pot&gt；_&lt；K，Ag&gt；=1.5)。具有增塑剂变化性质等功能的新型离子载体，由于考虑到它依赖于离子捕获位置的灵活性，因此利用熵效应判断重金属离子的识别也是可能的，并使其发展为席夫碱(23种)的Ag~+离子载体的函数表达式。较少

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