The Effects of Potential and pH on the Adsorption of Guanine on the Au(111) Electrode

The adsorption of nucleobase at a gold electrode has been a model system to study the interaction between biomolecule and metal, which is relevant to the development of sensors and molecular electronics. The current study has employed in situ scanning tunneling microscopy (STM) and voltammetry to investigate the adsorption configuration and spatial structure of guanine (G) on a well-defined Au(111) electrode in perchloric acid (HClO4) and neutral phosphate buffer solution (PBS) containing 50 mu M G. Potential control had a profound effect on the adsorption of the G molecule on the Au(111) electrode. No adsorption of G was observed at a potential more negative than 0 V in HClO4 and -0.2 V (versus Ag/AgCl) in PBS; shifting potential positively triggered a rapid adsorption of G to yield a well-ordered G array. Different spatial structures of G admolecules were imaged with STM in HClO4 and PBS, suggesting that ions in the electrolyte were important in this adsorption event. Shifting potential positively caused a more compact G adlayer with molecules adopting a tilted orientation. Meanwhile, G molecules continued to deposit on the Au(111) electrode leading to a multilayer G film. These processes were reversible to the potential modulation. G admolecules on the Au(111) electrode could be irreversibly oxidized in 0.1 M PBS, which resulted in a prominent peak at 0.74 V in the voltammogram. This oxidation process could be used to analyze the G molecule in a sample.