Electropolymerized Melamine on Electrochemically Reduced Graphene Oxide: Growth Mechanistics, Electrode Processing, and Amperometric Sensing of Acyclovir.

Metal-free, cost-efficient, redox-active electrode materials, combining graphene derivatives with nitrogen-rich polymelamine (PM), are widely explored as an interface layer for electrocatalysis and an electrochemical sensor platform. However, conventional chemical routes often yield derivatives of PM suffering from impaired redox behavior, restricting their electron-transfer kinetics. Herein, an optimal potentiodynamic method has been established to electrodeposit PM on electrochemically reduced graphene oxide (ErGO). A supporting electrolyte, containing Cl - , enhances the formation of intermediates NH 3 + and ═NH 2 + at the monomeric melamine, eventually interacting with the residual oxygenated functional groups of ErGO to form PM. In situ Raman spectrum analysis revealed the influence of the defective area and the graphitization ratio on the ErGO surface during the course of electropolymerization of melamine. Under optimal electrodeposition conditions ( E = 0-1.6 V; ν = 0.1 V/s), the amount of electrodeposited PM on the ErGO surface was determined to be 16.5 μg/(cycle·cm 2 ), using electrochemical quartz crystal microbalance analysis. An ErGO-PM-modified glassy carbon electrode (GCE) and a screen-printed electrode exhibit the direct electrooxidation of acyclovir (ACV). Amperometric analyses of ErGO-PM-modified electrodes exhibited the lowest detection limit of 137.4 pM with analytical robustness, rapid steady state, and reproducibility promising for ACV detection in complex biological matrices.