Electrically Enhanced Sensitivity (EES) of Ion-Selective Membrane Electrodes and Membrane-Based Ion Sensors

The use of external electronic enforcement in ion-sensor measurements is described. The objective is to improve the open-circuit (potentiometric) sensitivity of ion sensors. The sensitivity determines the precision of analyte determination and has been of interest since the beginning of ion-sensor technology. Owing to the theoretical interpretation founded by W.E. Nernst, the sensitivity is characterized by the slope and numerically predicted. It is empirically determined and validated during calibration by measuring an electromotive force between the ion sensor and the reference electrode. In practice, this measurement is made with commercial potentiometers that function as unaltered "black boxes". This report demonstrates that by gaining access to a meter's electrical systems and allowing for versatile signal summations, the empirical slope can be increased favorably. To prove the validity of the approach presented, flow-through ion-sensor blocks used in routine measurements of blood electrolytes (Na⁺, K⁺, Li⁺, Cl^-) and multielectrode probes with flat surfaces, similar to those applied previously for monitoring transmembrane fluxes of Na⁺, K⁺, Cl^- through living biological cells, are used. Several options to serve real-life electroanalytical challenges, including linear calibration for sensors with high-resistance membranes, responses with non-Nernstian slopes, non-linear calibration, and discrimination of nonfunctional sensors, are shown.