Controlled formation of thiol and disulfide interfaces.

The work reported herein describes the controlled creation of uniform thiol-functionalized siloxane-anchored self-assembled monolayers (SAMs) and their selective transformation into intramonolayer (bridging) disulfides. These disulfides provide for the efficient immobilization of (bio)molecules bearing pendant thiols or disulfides, with no need for added oxidant. The unambiguous development of this surface chemistry required analytical methods that distinguish thiol and disulfide moieties on a surface.

Variations in the structure and reactivity of thioester functionalized self-assembled monolayers and their use for controlled surface modification.

Thioester-functionalized, siloxane-anchored, self-assembled monolayers provide a powerful tool for controlling the chemical and physical properties of surfaces. The thioester moiety is relatively stable to long-term storage and its structure can be systematically varied so as to provide a well-defined range of reactivity and wetting properties. The oxidation of thioesters with different-chain-length acyl groups allows for very hydrophobic surfaces to be transformed into very hydrophilic, sulfonic acid-bearing, surfaces.