Solid-contact
ion-selective electrodes (SC-ISEs) in direct long-term
contact with physiological samples must be biocompatible and resistant
to biofouling, but most wearable SC-ISEs proposed to date contain
plasticized poly(vinyl chloride) (PVC) membranes, which have poor
biocompatibility. Silicones are a promising alternative to plasticized
PVC because of their excellent biocompatibility, but little work has
been done to study the relationship between silicone composition and
ISE performance. To address this, we prepared and tested K+ SC-ISEs with colloid-imprinted mesoporous (CIM) carbon as the solid
contact and three different condensation-cured silicones: a custom
silicone prepared in-house (Silicone 1), a commercial
silicone (Dow 3140, Silicone 2), and a commercial fluorosilicone
(Dow 730, Fluorosilicone 1). SC-ISEs prepared with each
of these polymers and the ionophore valinomycin and added ionic sites
exhibited Nernstian responses, excellent selectivities, and signal
drifts as low as 3 μV/h in 1 mM KCl solution. All ISEs maintained
Nernstian response slopes and had only very slightly worsened selectivities
after 41 h exposure to porcine plasma (log K
K,Na values of −4.56, −4.58, and −4.49,
to −4.04, −4.00, and −3.90 for Silicone
1, Silicone 2, and Fluorosilicone 1, respectively), confirming that these sensors retain the high selectivity
that makes them suitable for use in physiological samples. When immersed
in porcine plasma, the SC-ISEs exhibited emf drifts that were still
fairly low but notably larger than when measurements were performed
in pure water. Interestingly, despite the very similar structures
of these matrix polymers, SC-ISEs prepared with Silicone 2 showed lower drift in porcine blood plasma (−55 μV/h,
over 41 h) compared to Silicone 1 (−495 μV/h)
or Fluorosilicone 1 (−297 μV/h).