Reference Electrodes Based on Ionic Liquid-Doped Reference Membranes with Biocompatible Silicone Matrixes

Many reference electrodes with an ionic liquid-doped reference membrane contain a plasticizer that can gradually leach out into the sample. However, because many common plasticizers are known to be endocrine disruptors and may induce inflammatory reactions, they are preferably avoided for wearable or implantable sensors. Therefore, this work tested polymeric reference electrode membranes prepared by solvent casting from seven commercially available biocompatible silicones that are widely used in implantable devices. Only reference electrodes with membranes consisting of poly(3,3,3-trifluoropropylmethylsiloxane) (Fluorosilicone 1) and one of several 1-methyl-3-alkylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids provided a stable and sample-independent potential in electrolyte solutions spanning the range of electrolyte concentrations in human blood, with more hydrophobic ionic liquids performing better. Over 8 days at 37 °C in artificial blood electrolyte solutions, the reference membranes doped with 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide exhibited a potential drift as low as 20 μV/h. In 10% animal serum, a 112 μV/h drift was observed over 5.8 days. The other six silicone materials doped with an ionic liquid either failed to form self-standing membranes or did not provide a sample-independent potential in the ionic concentration range tested. In case of the functional reference electrodes, differential scanning calorimetry confirmed good miscibility between the ionic liquid and the polymer matrix, whereas the poor miscibility of four polymer matrixes and the ionic liquids - as confirmed by differential scanning calorimetry - correlated with an undesirable sample dependence of the reference potential.