The present work describes the construction of nanoporous assemblies based on single self-assembled monolayer (SAM) of mono-(6-deoxy6-mercapto)-beta-cyclodextrin (PCDSH) and two-component monolayers of PCDSH and 11-mercaptoundecanoic acid. An investigation of its supramolecular properties toward the tricyclic antidepressants drugs chlorprothixene and imipramine is also presented. The adsorption process was investigated by using surface plasmon resonance and the selectivity of the SAM was verified by using electroactive species permeable and not permeable into the cyclodextrin SAM, such as ferrocenemonocarboxylic acid, hexacyanoferrate, methylene blue and hexamineruthenium (II). The redox probe was chosen based on its capability to permeate the grafted cyclodextrin molecules and its electrochemical characteristics. It was applied to imipramine and chlorprothixene competitive assay by the mono-(6-deoxy-6-mercapto)-beta-cyclodextrin self-assembled cavity. Finally, the pK(a) of the surface and its effects on thee host-guest interaction properties were also investigated. (c) 2007 Elsevier Ltd. All rights reserved.