Hydrogels Doped with Redox Buffers as Transducers for Ion-Selective Electrodes

Solid-contact ion-selective electrodes (ISEs) with an unintentional water layer between the sensing membrane and underlying electron conductor are well known to suffer from potential drift caused by the instability of the phase boundary potential between the sensing membrane and the water layer with its uncontrolled ionic composition. The reproducibility and long-term emf stability of ISEs with a miniaturized inner filling solution comprising a hydrogel and a hydrophilic electrolyte have not been studied as thoroughly. Here, such devices are discussed with a view to electrode-to-electrode reproducibility, using both hydrophilic ion-exchange and plasticized PVC membranes, along with a hydrophilic redox buffer composed of ferrocyanide and ferricyanide to control the potential between the hydrogel and the underlying electron conductor. With plasticized PVC sensing membranes, these electrodes showed an E0 reproducibility of ±1.1 mV or better, while with hydrophilic ion-exchange membranes, this variability was slightly larger. Long-term drifts were also assessed with both membranes, and the effect of osmotic pressure on drift was shown to be insignificant for the PVC membranes and very small at most for the hydrophilic membranes.