Analytical Sciences

Potassium-Selective Membrane Electrodes Based on Macrocyclic Metacyclophanes Analogous to Calixarenes

Takashi KATSU,* Yuutaku YOKOYAMA,* Keisuke UEDA,* Kazufumi KOHNO,** and Takehiko YAMATO**

*Faculty of Pharmaceutical Sciences, Okayama University, Tsushima, Okayama 700-8530, Japan
**Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Saga 840-8502, Japan

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 NH₃⁺ 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⁺.

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