The electro-oxidation of alternariol monomethyl ether (AME), one of the main metabolites of the Alternaria genus mycotoxins, is studied at 1-dodecanethiol (DDT)-modified gold electrodes, in acetonitrile (ACN) -aqueous phosphate buffer solutions of different pH values, by using cyclic (CV) and square-wave (SWV) voltammetries. The AME voltammetric response at the bare electrode suffers from two drawbacks: it appears at potentials close to the onset of gold oxide formation, and it is hampered by a fouling of the electrode surface due to the accumulation of oxidized products. These shortcomings are circumvented by the use of DDT-coated electrodes. since the intervening monolayer inhibits gold oxide formation and surface passivation by the electrochemical products, without affecting the oxidation kinetics of AME significantly. Diagnostic criteria based on the voltammetric peak parameters show that the electrochemical behavior of AME at the modified electrode is mainly controlled by reactant diffusion from solution, with a weak adsorption of both the mycotoxin and its oxidation products at monolayer defects. Calibration curves were constructed from the AME square-wave voltammetric response and a detection limit of 9.1 x 10(-8) mol dm(-3) was determined, which is about three times smaller than a previous estimate at platinum and glassy carbon electrodes, and about fifty times smaller than the limit derived from measurements carried out at a polyphenol oxidase-modified carbon paste electrode. (C) 2004 Elsevier B.V. All rights reserved.