Potassium-Selective Membrane Electrodes Based on Macrocyclic Metacyclophanes Analogous to Calixarenes
Potassium-Selective Membrane Electrodes Based on Macrocyclic Metacyclophanes Analogous to Calixarenes
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DOI：
10.2116/analsci.21.175
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发表时间：
2005-02
影响因子：
1.6
通讯作者：
T. Katsu;Y. Yokoyama;Keisuke Ueda;Kazufumi Kohno;T. Yamato
中科院分区：
文献类型：
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作者：
T. Katsu;Y. Yokoyama;Keisuke Ueda;Kazufumi Kohno;T. Yamato
由9,16,25,32-四羟基[3.1.3.1]元环烷衍生的四丁基酯是构建K^+选择性膜电极的优良离子载体。该离子载体对K^+的选择性远高于结构相似的钾离子载体IV。特别是有机铵离子的干扰明显减小。钾离子载体IV在环结构中含有氧原子，而现在的离子载体将氧原子变成了碳原子。因此，去除环上氧原子可以减少与有机铵离子NH_3^+基团的相互作用。该离子载体的空腔大小介于杯[4]芳烃和杯[6]芳烃衍生物（分别作为Na^+和Cs^+离子载体）之间，表明其对碱金属阳离子的识别能力与空腔大小密切相关。该K^+选择性电极受Rb^+和Cs^+的干扰较小，但受Na^+的干扰较大。
The tetrabutyl ester derived from 9,16,25,32-tetrahydroxy[3.1.3.1]metacyclophane was an excellent ionophore for constructing a K^+-selective membrane electrode. This ionophore exhibited a much higher selectivity toward K^+ than the structurally similar potassium ionophore IV commercially available from Fluka. In particular, the interference from organic ammonium ions decreased remarkably. Potassium ionophore IV possessed oxygen atoms in the ring structure, while the present ionophore changed the oxygen atoms to carbon atoms. Thus, the removal of oxygen atoms in ring constituents of the metacyclophane acted to reduce the interaction with the NH_3^+ group of organic ammonium ions. The size of the cavity of the present ionophore was between those of calix[4]arene and calix[6]arene derivatives, which act as Na^+ and Cs^+ ionophores, respectively, demonstrating that the ability to recognize alkali metal cations was strongly cavity size-dependent. The present K^+-selective electrode had less interference from Rb^+ and Cs^+ than an electrode constructed using valinomycin, but suffered greater interference from Na^+.