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A novel method to readily determine the lipophilicity of electrogenerated charged species is reported. This is achieved by local electrolysis at a Pt coated micropipette and, subsequently, driving the electrogenerated species to transfer across the liquid–liquid interface supported at the tip of the micropipette under potential control. The formal potential of ion transfer can then be used to give a measure of its relative lipophilicity. The method proposed is facile and enables the study of potentially unstable charged products of electron transfer reactions. [Copyright &y& Elsevier]

The article investigates electron transfer kinetics between a solution redox mediator and the nanocrystal core using a monolayer of alkanethiolate protected gold nanocrystals and reports the first quantitative estimate for the rate of electron transfer at the nanocrystal/solution interface. The rate of electron transfer was found to be depended on the redox couple used, which shows the importance of molecule specific properties such as the effect of their relative hydrophilicities.

This article reports on the ion permeability of self-assembled monolayers (SAMs) formed on the surface of charged alkanethiol-protected gold nanoparticles, so-called monolayer-protected clusters (MPCs). The capacitance and thus the charging energy required to add/remove an electron from the metal core are extremely sensitive to ions entering the monolayer, and the extent of ion penetration can be tuned by the charge and size of the ions and the permittivity of the solvent. Experimentally, this effect is comparable to ion association with conventional redox molecules, indicating that MPCs despite their large size and the fundamentally differing nature of the electron transfer process can be treated analogously to redox molecules. [ABSTRACT FROM AUTHOR]