Protonation and deprotonation of cysteine and cystine monolayers probed by impedance spectroscopy

The desorption mechanism for electrochemically-formed self-assembled monolayers from cysteine and cystine on a Au(1 1 1) electrode was investigated. The monolayer desorption in 0.1 M KClO4 is found to occur in two steps with differing potentials. At potentials more positive than the desorption potential (circa −0.65 V vs. SCE), a quasi-reversible process, assigned to protonation/deprotonation, is observed. This process is found to occur at very discreet potentials when cysteine monolayers are probed by impedance spectroscopy. Monolayers derived from the disulfide (cystine) are found to protonate/deprotonate over a wider potential range. This suggests that electrochemically-formed monolayers obtained from disulfides do not afford the same level of organization as those derived from thiol species. The value of the double layer capacitance increases from 15 to 30 μF cm−2 after deprotonation. This suggests that the adsorption of cysteine weakens following the deprotonation. As expected, the protonation/deprotonation step is pH dependent and it is not observed in strong basic medium (0.1 M NaOH).