Electrochemistry in a Two- or Three-Electrode Configuration to Understand Monopolar or Bipolar Configurations of Platinum Bionic Implants

Electrodes are used in vivo for chemical sensing, electrophysiological recording, and stimulation of tissue. The electrode configuration used in vivo is often optimised for a specific anatomy and biological or clinical outcomes, not electrochemical performance. Electrode materials and geometries are constrained by biostability and biocompatibility issues and may be required to function clinically for decades. We performed benchtop electrochemistry, with changes in reference electrode, smaller counter-electrode sizes, and three- or two-electrode configurations. We detail the effects different electrode configurations have on typical electroanalytical techniques used on implanted electrodes. Changes in reference electrode required correction by application of an offset potential. In a two-electrode configuration with similar working and reference/counter-electrode sizes, the electrochemical response was dictated by the rate-limiting charge transfer step at either electrode. This could invalidate calibration curves, standard analytical methods, and equations, and prevent use of commercial simulation software. We provide methods for determining if an electrode configuration is affecting the in vivo electrochemical response. We recommend sufficient details be provided in experimental sections on electronics, electrode configuration, and their calibration to justify results and discussion. In conclusion, the experimental limitations of performing in vivo electrochemistry may dictate what types of measurements and analyses are possible, such as obtaining relative rather than absolute measurements.

Automated summary

Electrodes used in vivo are often optimized for specific anatomies and outcomes rather than electrochemical performance. Their materials and geometries are limited by biostability and biocompatibility, with the requirement to function for long periods clinically. This study investigates the effects of different electrode configurations on electroanalytical techniques used on implanted electrodes, providing methods for assessing their impact on in vivo electrochemical response.