Self assembled monolayers (SAMs) of 11-mercaptoundecanoic acid (MUA) and 11-amino-1-undecanethiol (AUT) were prepared on gold electrodes. The SAMs were investigated by differential pulse voltammetry (DPV), cyclic voltammetry (CV) and rotating disk voltammetry (RDV) using [Fe(CN)(6)](3-),[Fe(CN)(6)](4-) and Ru(NH3)(6)(3+) as electroactive marker ions, and La3+, Ca2+,1,3,7-naphthalene trisulfonate (NTS3-), N,N'-dihydroxyethyl-4,4'-bipyridinium (Vi(o++)), 1-ferrocenylethanol and ferrocenealdehyde as ion-gate promoters, surface site competing ions, and/or electrocatalysts. The current densities at the SAM-modified electrodes correlate with three types of simple interactions, i.e., charge-equal charge, charge-uncharged, and charge-opposite charge. More detailed investigations revealed: (i) strong counter ion binding of multiply charged electroactive or non-electroactive ions to the oppositely charged SAM head groups; (ii) competition between equally charged ions for such surface sites; (iii) electrocatalysis of electron transfer by surface confined electroactive marker ions to redox species in solution including quantitative electron transfer rates by analysis of Koutecky -Levich plots; (iv) apparent charge inversion of the SAM head groups by surface confinement of a multiply charged counter ion; (v) build-up of a second layer of multiply charged electroactive ions at the charge-inverted SAM; (vi) competing electron transfer through the inner and outer layer at the charge inverted SAM. This insight allows for a more detailed understanding of the principles of signal amplification in ion gate sensors. (C) 2004 Elsevier B.V. All rights reserved.