Surfactants for Optode Emulsion Stabilization without Sacrificing Selectivity or Binding Constants

We compare here the effect of surfactants on ion-selective membranes measured via voltammetry and optode emulsions measured optically. Cyclic voltammetry on a thin-film ion-selective membrane is shown to be a useful screening technique for the estimation of effective complex formation constants and selectivity coefficients for different surfactants with various cations. This technique is particularly useful for its ability to identify separate ion-transfer events (free, surfactant complexed, ionophore complexed) for a specific membrane. However, we also caution against the over-reliance on this technique as changes in membrane characteristics are observed following surfactant partitioning. Of the surfactants explored here, a zwitterionic sulfobetaine-based surfactant was found to stabilize sensors without reducing effective binding constants and selectivity, with greatly superior characteristics to other commonly utilized surfactants. Those include Brij-35, F-127, and Triton X-100, all of which showed significant binding to so-called free ions in the membrane, resulting in peak potential shifts of 199 +/- 10, 180 +/- 24, 278 +/- 11 mV, respectively, for potassium following the subtraction of transducing layer effects. This peak shift translated to a much larger undesired free ion response in optode emulsions. The selectivity in emulsion-based systems was also shown to decrease in the presence of nonionic surfactants compared to that containing the zwitterion.