Strong Interaction between Imidazolium-Based Polycationic Polymer and Ferricyanide: Toward Redox Potential Regulation for Selective In Vivo Electrochemical Measurements

This study effectively demonstrates a strategy to enable the ferricyanide-based second-generation biosensors for selective in vivo measurements of neurochemicals, with glucose as an example. The strategy is based on regulation of redox potential of ferricyanide mediator by carefully controlling the different adsorption ability of ferricyanide (Fe(CN)(6)(3-)) and ferrocyanide (Fe(CN)(6)(4-)) onto electrode surface. To realize the negative shift of the redox potential of Fe(CN)(6)(3-/4-), imidazolium-based polymer (Pim) is synthesized and used as a matrix for surface adsorption of Fe(CN)(6)(3-/4-) due to its stronger interaction with Fe(CN)(6)(3-) than with Fe(CN)(6)(4-). The different adsorption ability of Fe(CN)(6)(3-) and Fe(CN)(6)(4-) onto electrodes modified with a composite of Pim and multiwalled carbon nanotubes (MWNTs) eventually enables the stable surface adsorption of both species to generate integrated biosensors and, more importantly, leads to a negative shift of the redox potential of the surface-confined redox mediator. Using glucose oxidase (GOD) as the model biorecognition units, we demonstrate the validity of the ferricyanide-based second-generation biosensors for selective in vivo neurochemical measurements. We find that the biosensors developed with the strategy demonstrated in this study can be used well as the selective detector for continuous online detection of striatum glucose of guinea pigs, by integration with in vivo microdialysis. This study essentially paves a new avenue to developing electrochemical biosensors effectively for in vivo neurochemical measurements, which is envisaged to be of great importance in understanding the molecular basis of physiological and pathological events.