The adsorption/desorption behaviour of the thiol/disulfide redox couple, cysteine/cystine, was monitored at a Au(1 1 1) single crystal electrode. The monolayers were formed electrochemically from 0.1 M KClO4 and 0.1 M NaOH solutions containing either the thiol or the disulfide. Distinct features in the adsorption potential were noted. An adsorption peak was observed in the cyclic voltammograms (CVs) from Au(1 1 1) in 0.1 M KClO4 solutions containing cystine at -0.57 V vs. saturated calomel electrode. Under the same conditions, the CVs from solutions containing cysteine showed an adsorption peak at -0.43 V (0.14 V more positive than the corresponding peak from disulfide solutions). This showed that the thiol and disulfide species have different adsorption properties. Similar behaviour was observed in 0.1 M NaOH. Cyclic voltammetric and chronocoulometric data were employed to determine the surface coverage of the different monolayers. Cysteine solutions prepared in 0.1 M KClO4 provided coverages of 3.0 x 10(-10) and 2.5 x 10(-10) mol cm(-2) for the L and the D-L species, respectively as evaluated from the desorption peaks. Desorption of cystine in the same medium yielded coverages of 1.2 x 10(-10) mol cm(-2) for both L and D-L solutions (or 2.4 x 10(-10) mol cm(-2) in cysteine equivalents). Surface coverages obtained from Au(1 1 1) in 0.1 M NaOH corresponded to 3.9 x 10(-10) mol cm-2 for L-cysteine, and 1.2 x 10(-10) mol cm(-2) (or 2.4 x 10(-10) mol cm(-2) cysteine equivalents) for L and D-L cystine. (C) 2003 Elsevier Science B.V. All rights reserved.