Preparation and Characterization of Dendrimer Monolayers and Dendrimer−Alkanethiol Mixed Monolayers Adsorbed to Gold

Abstract

Single-component monolayers of dendrimers and two-component monolayers consisting of dendrimers and n-alkanethiols immobilized on Au substrates are described. Single-component monolayers are prepared by exposing an Au substrate to ethanolic solutions of amine- or hydroxy-terminated polyamidoamine (PAMAM) dendrimers. The resulting monolayers are highly stable and nearly close-packed for dendrimer generations ranging from 4 to 8 (G4−G8). Electrochemical ac-impedance measurements indicate that the dendrimer surface is very porous toward the electroactive redox couple Fe(CN)63-/4-. Ferrocene-terminated dendrimer monolayers have also been investigated. Exposure of higher-generation dendrimer monolayers to ethanolic solutions of hexadecanethiol (C16SH) results in a dramatic compression of the dendrimers, and causes them to reorient on the surface from an oblate to prolate configuration. The dendrimers originally present on the surface do not desorb as a consequence of this configurational change. Comparison of the extent of adsorption of C16SH in different media (vapor-phase N2, hexane, and ethanol) shows that solvation of the dendrimers is the primary driving force for the structural change. Finally, the reactivity and stability of the dendrimer monolayers is investigated by on-surface functionalization of the dendrimer monolayer with 4-(trifluoromethyl)benzoyl chloride. The physical and chemical properties of the single- and two-component monolayers are evaluated by using reflection infrared spectroscopy, ellipsometry, contact-angle measurements, ac-impedance spectroscopy, cyclic voltammetry, and surface acoustic wave (SAW)-based analyte-dosing experiments.