Covalently grafted KolliphorEL (a poly(ethylene glycol)-based transporter molecule for hydrophobic water-insoluble drugs; MW, ca. 2486; diameter, ca. 3 nm) at the surface of a glassy-carbon electrode strongly affects the rate of electron transfer for aqueous redox systems such as Fe(CN)6(3-/4-). XPS data confirm monolayer grafting after electrochemical anodization in pure KolliphorEL. On the basis of voltammetry and impedance measurements, the charge transfer process for the Fe(CN)6(3-/4-) probe molecule is completely blocked after KolliphorEL grafting and in the absence of a "guest". However, in the presence of low concentrations of suitable ferrocene derivatives as guests, mediated electron transfer across the monolayer via a shuttle mechanism is observed. The resulting amplification of the ferrocene electroanalytical signal is investigated systematically and compared for five ferrocene derivatives. The low-concentration electron shuttle efficiency decreases in the following sequence: (dimethylaminomethyl)ferrocene > n-butyl ferrocene > ferrocene dimethanol > ferroceneacetonitrile > ferroceneacetic acid.
Keywords: Cremophor; PEGylation; amplification; sensor; tunneling; voltammetry.