Antifouling Coatings Generated from Unsymmetrical Partially Fluorinated Spiroalkanedithiols

[Image: see text] Biofouling negatively impacts modern society on a daily basis, especially with regard to the important industries of medicine, oil, and shipping. This manuscript describes the preparation and study of model antifouling coatings generated from the adsorption of unsymmetrical partially fluorinated spiroalkanedithiols on gold. The antifouling properties of the self-assembled monolayers (SAMs) derived from the spiroalkanedithiols were compared to SAMs derived from analogous monodentate partially fluorinated and nonfluorinated alkanethiols. The antifouling properties were evaluated using in situ surface plasmon resonance spectroscopy (SPR), ex situ electrochemical quartz crystal microbalance (QCM) measurements, and ex situ ellipsometric thickness measurements. The resistance to nonspecific protein adsorption of the SAMs was evaluated with proteins having a wide range of properties and applications including protamine, lysozyme, bovine serum albumin, and fibrinogen. The results from the SPR and the QCM measurements demonstrated that in most cases, the SAM coatings derived from the partially fluorinated spiroalkanedithiols having mixed hydrocarbon and fluorocarbon tail groups exhibited better antifouling performance when compared to the SAMs derived from their single-component monodentate counterparts. The studies also revealed that while the SPR and the QCM measurements in most cases were able to distinguish the adsorption trends for the SAMs and proteins examined, the ellipsometric thickness measurements were markedly less discriminating. On the whole, these studies validate the use of unsymmetrical partially fluorinated spiroalkanedithiols for generating effective antifouling coatings on metal substrates.