Nanoporous Carbon Materials as Solid Contacts for Microneedle Ion-Selective Sensors

Continuous sensing of biomarkers, such as potassium ions or pH, in wearable patches requires miniaturization of ion-selective sensor electrodes. Such miniaturization can be achieved by using nanostructured carbon materials as solid contacts in microneedle-based ion-selective and reference electrodes. Here we compare three carbon materials as solid contacts: colloid-imprinted mesoporous (CIM) carbon microparticles with ∼24-28 nm mesopores, mesoporous carbon nanospheres with 3-9 nm mesopores, and Super P carbon black nanoparticles without internal porosity but with textural mesoporosity in particle aggregates. We compare the effects of carbon architecture and composition on specific capacitance of the material, on the ability to incorporate ion-selective membrane components in the pores, and on sensor performance. Functioning K⁺ and H⁺ ion-selective electrodes and reference electrodes were obtained with gold-coated stainless-steel microneedles using all three types of carbon. The sensors gave near-Nernstian responses in clinically relevant concentration ranges, were free of potentially detrimental water layers, and showed no response to O₂. They all exhibited sufficiently low long-term potential drift values to permit calibration-free, continuous operation for close to 1 day. In spite of the different specific capacitances and pore architecture of the three types of carbon, no significant difference in potential stability for K⁺ ion sensing was observed between electrodes that used each material. In the observed drift values, factors other than the carbon solid contact are likely to play a role, too. However, for pH sensing, electrodes with CIM as a carbon solid contact, which had the highest specific capacitance and best access to the pores, exhibited better long-term stability than electrodes with the other carbon materials.