Electrochemical properties of a gold electrode modified with a mixed monolayer

The electrochemical properties of a gold electrode modified with a mixed thiol monolayer containing both a polar and a non-polar head group have been investigated in aqueous Fe(CN)₆^4?, flavin adenine dinucleotide (FAD) and ubiquinone-0 (2,3-dimethoxy-5-methyl-1,4-benzoquinone, UQ₀) solutions. The cyclic voltammetric current-potential (i-E) response of Fe(CN)₆^4? was found to be affected considerably by the polarity of the head group contained in the mixed monolayer assembly, as compared with those of FAD and UQ₀. It was also found that in the cases of UQ₀ and FAD the i-E responses for the modified electrode were affected by their own molecular size rather than the polarity of the mixed monolayer head group. Furthermore, compared with Fe(CN)₆^4? ion, these biologically related molecules are able to permeate readily into the well-organized and hydrophobic alkyl chains of the monolayer assembly. The voltammetric profile of UQ₀ was improved by the modification of aminoethanethiol, as compared with those of bare gold and the electrode modified with other polar thiols. Further, two different permeation paths of the electrode species into the mixed monolayer are suggested from the variation of the i-E response with the cycle of the potential scan.