Mercuracarborand “Anti-Crown Ether”-Based Chloride-Sensitive Liquid/Polymeric Membrane Electrodes

Abstract

Highly sensitive and selective chloride liquid/polymeric membrane electrodes are described that employ [9]mercuracarborand-3 (MC3), a neutral preorganized macrocyclic Lewis acid, as the anion carrier. MC3-based chloride-sensitive membrane electrodes, doped with different mole percentages of cationic additives (5, 10, and 60 mol % tridodecylmethylammonium chloride) relative to the amount of the carrier, exhibit enhanced potentiometric selectivity for chloride over other anions, including more lipophilic anions such as perchlorate, nitrate, and thiocyanate. In addition, the selectivity coefficients obtained are shown to meet the requirement for clinical applications. The obtained selectivity pattern is shown to correlate very well with ¹⁹⁹Hg NMR titrations of MC3 with various anions, performed in organic solvents. Optimized membrane electrodes show a near-Nernstian response toward chloride over a wide concentration range and have micromolar detection limits. MC3-based chloride sensors show a fast response time (in the order of few seconds), as well as short recovery time. The developed mercuracarborand-based sensors do not practically respond to pH changes over the pH range of 2.5−7.0. Response characteristics (e.g., detection limit, linear range, response slope, and selectivity) of the [9]mercuracarborand-3 based chloride sensors remain essentially the same over a period of ∼2 months, reflecting remarkable stability and well-defined chemistry of the macrocyclic Lewis acid ionophore.