Electrochemical nano-roughening of gold microstructured electrodes for the enhanced detection of copper and glucose

One of the main challenges for electrochemical sensor miniaturization is the fabrication of electrodes with a smaller footprint, while maintaining, or even increasing, their sensitivity for the targeted application. Our research group has previously demonstrated the enhancement of the electroactive surface area of gold electrodes up to 6-fold, relative to planar gold electrodes with the same footprint, through the generation of a wrinkled thin film surface via thermal shrinking. In this work, the electroactive surface area of wrinkled gold electrodes was further enhanced up to 5-fold (30-fold over flat electrodes) using a chronoamperometric pulsing technique. Scanning electron microscopy images showed progressive increase of surface roughness in response to an increasing number of applied pulses. The resulting nanoroughened electrodes present several advantages in addition to the enhanced electroactive surface area. These electrodes offer superior fouling resistance compared to that of wrinkled and flat electrodes when submerged in a solution containing bovine serum albumin at high concentrations. Cyclic voltammetry data also revealed greater sensitivity of nanoroughened electrodes toward anodic copper stripping, where the limit of quantification of copper by the nano-roughened electrodes was 0.3 ppm. Nano-roughened electrodes also allowed the highly sensitive enzyme-free detection of glucose through chronoamperometry, with a limit of detection of 0.5 mM, whereas planar electrodes did not demonstrate any ability to oxidize glucose. We foresee that this methodology to fabricate nanostructured electrodes will accelerate the development of simple, cost-effective and high sensitivity electrochemical platforms.