Cesium ion-selective electrodes based on 1,3-alternate thiacalix[4]biscrown-6,6

Four thiacalix[4]biscrown ethers with 1,3-altemate conformation were examined for the potentiometric responses in poly(vinyl chloride) membrane electrodes. Their potentiometric selectivities toward potassium and cesium ions over other alkali, alkaline earth, and transition metal ions were measured by the fixed interference method (FIM). Among the ionophores, 1,3-alternate thiacalix[4]biscrown-6,6 showed a high selectivity for cesium over potassium ion and so was optimized as a Cs+-selective electrode. The electrode exhibited a linear response with a near Nernstian slope of 57.6 mV per decade in the concentration range of 1.0 x 10(-6) to 3.2 x 10(-2) M. It was suitable for use in aqueous solution in a wide range of pH 2.5-12.5 and had a fast response time of ca. 5 s. On the basis of 1,3-alternate thiacalix[4]biscrown-6,6, the electrode has a wide linear range and selectivity for cesium ion over potassium ion (log K-Cs(+),K+ = -3.7) better than those previously reported with other ionophores. (C) 2004 Elsevier B.V. All rights reserved.