Individual Nanotube-Based Needle Nanoprobes for Electrochemical Studies in Picoliter Microenvironments

We report the fabrication and characterization of individual nanotube-based, long and straight needle nanoprobes for electrochemistry and the study of their applicability and behavior in microenvironments. The needle nanoprobe, with a nanoscale ring-shaped Au electrode at the tip of the needle serving as the active electrode, was characterized by electrochemical current measurement and cyclic voltammetry and analyzed with electrochemical models. Such a needle nanoprobe, in combination with another metal-coated nanowire as a reference electrode, was further used, for the first time, for local electrochemical sensing inside microdroplets having volumes down to a few picoliters. We explain the acquired voltammetric behaviors of redox-active molecules in confined microscale environments and reveal a unique electrochemical mechanism which allows the regeneration of the redox-active molecules and the establishment of a stable reference potential in the microenvironments.