Electrochemical studies of derivatized thiol self-assembled monolayers on gold electrode in the presence of surfactants.

Electrochemical impendence spectroscopy (EIS), cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were performed to investigate the barrier properties and electron transfer of derivatized thiol self-assembled monolayers (SAMs) on gold in the presence of surfactants. The thiol derivatives used included 2-mercaptoethanesulfonic acid (MES), 2-mercaptoacetic acid (MAA), and N-acetyl-L-cysteine (NAC). A simple equivalent circuit was derived to fit the impedance spectra very well. The negative redox probe [Fe(CN)6](3-/4-) was selected to indicate the electron-transfer efficiency on the interface of the studied electrodes. It was found that by changing the surface structure of SAMs, different surfactants could regulate the barrier properties and electron-transfer efficiency in different ways. A positively charged surfactant lowered the electrostatic repulsion between the negative redox probe and negatively charged surface groups of a monolayer, while enhancing the reversibility of electron transfer by virtue of increasing the redox probe concentration within the electric double-layer region. A neutral surfactant showed no significant effect, while a negative surfactant hindered the access and reaction of redox probe by electrostatic repulsion of same-sign charges.