Pulsed amperometric detection of underivatized amino acids using polypyrrole modified copper electrode in acidic solution

The successful pulsed amperometric detection of underivatized amino acids have been carried out in an acidic media on a polypyrrole (PPy) modified Cu electrode. The formation of PPy film doped with glutamate (glu) on a Cu electrode surface changes the mechanism of Cu dissolution. After application of multistep potential waveform, the PPy film was glu free due to the electro-reduction and overoxidation. High anodic potential polarization treatment yielded partially overoxidized PPy film as long as the Cu surface dissolution and amino acid permeation through the film was well controlled. This overoxidized PPy film acted as a charge and size exclusion barrier in order to improve the selectivity and stability of a Cu electrode. Various process parameters such as film modification time, detection and cleaning potential and pH of solution have been optimized to maximize the beneficial electrocatalytic properties of the electrode surface. At an optimized condition, detection limits for positively charged histidine and arginine are 19 and 22 pg respectively, whereas the neutral amino acids detected in amounts of 0.9–2.3 ng. Furthermore, the PPy coated Cu electrode response was long lived, stable and reproducible.