Potentiometric evaluation of calix[4]arene anion receptors in membrane electrodes: phosphate detection.

Ion-selective membrane electrodes doped with the urea- or thiourea-functionalised calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis[[4-N'-(phenylureido)butyl]oxy]-26,28-dipropoxy calix[4]arene (I) and 5,11,17,23-tetra-tert-butyl-25,27-bis[[4-(N'-phenylthioureido)-butyl]oxy]-26,28-dipropoxy calix[4]arene (II), were evaluated for anion sensing. Potentiometric results show that these calixarene ionophore-based membrane electrodes exhibit a good sensitivity to aqueous solutions of the monohydrogen orthophosphate species HPO(4)(2-) in the concentration range 5.0 x 10(-5) to 1.0 x 10(-1)M, with near-Nernstian response slopes of -33.0 and -28.0 mV dec(-1) for ionophores I and II, respectively. Selectivity coefficient values for monohydrogen orthophosphate over a range of common anions were determined by the fixed interference and matched potential methods and indicated that these membrane electrodes exhibit a good selectivity for HPO(4)(2-) with respect to the other anions, including sulfate and nitrate.