Article révisé par les pairs
Résumé : Oligo(ethylene glycol) films are known to be very efficient at reducing the non-specific adsorption of biomacromolecules on surfaces, but they often show a tendency to decrease drastically the rate of heterogeneous electron transfer at the modified surface, making them unsuitable for electrochemical biosensing. In this work, the heterogeneous electron transfer across the self-assembled monolayer of a short thiolated oligo(ethylene glycol) is investigated using four redox systems: [Fe(CN)6]3−/4−, [Ru(NH3)6]3+/2+, Fc(MeOH)2+/0 and [IrCl6]2−/3−. Fast electron transfer kinetics are evidenced in all cases except the ferri/ferrocyanide couple, for which the electron transfer is completely suppressed. Interfacial characterizations by means of spectroscopic ellipsometry, electrochemical desorption experiments and capacity measurements indicate that the film consists of a fairly hydrated single monolayer with a surface concentration of 4.1 × 10−10 mol cm−2. The peculiar behavior of [Fe(CN)6]3−/4− is discussed in terms of the hydration properties of both the monolayer and the electroactive anions. Interestingly, the self-assembled monolayer exhibits the desired antifouling properties against protein adsorption, tested with bovine serum albumin, making this system a promising platform for the development of electrochemical biosensors.