title: Robust Maleimide-Functionalized Gold Surfaces and Nanoparticles Generated Using Custom-Designed Bidentate Adsorbates.
abstract: A series of custom-designed alkanethioacetate ligands were synthesized to provide a facile method of attaching maleimide-terminated adsorbates to gold nanostructures via thiolate bonds. Monolayers on flat gold substrates derived from both mono- and dithioacetates, with and without oligo(ethylene glycol) (OEG) moieties in their alkyl spacers, were characterized using X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, ellipsometry, and contact angle goniometry. For all adsorbates, the resulting monolayers revealed that a higher packing density and more homogeneous surface were generated when the film was formed in EtOH, but a higher percentage of bound thiolate was obtained in THF. A series of gold nanoparticles (AuNPs) capped with each adsorbate were prepared to explore how adsorbate structure influences aqueous colloidal stability under extreme conditions, as examined visually and spectroscopically. The AuNPs coated with adsorbates that include OEG moieties exhibited enhanced stability under high salt concentration, and AuNPs capped with dithioacetate adsorbates exhibited improved stability against ligand exchange in competition with dithiothreitol (DTT). Overall, the best results were obtained with a chelating dithioacetate adsorbate that included OEG moieties in its alkyl spacer, imparting improved stability via enhanced solubility in water and superior adsorbate attachment owing to the chelate effect.
authors.affiliation: Department of Chemistry and the Texas Center for Superconductivity, University of Houston , 4800 Calhoun Road, Houston, Texas 77204-5003, United States.
authors.forename: Chul Soon
authors.initials: CS
authors.lastname: Park
authors.affiliation: Department of Chemistry and the Texas Center for Superconductivity, University of Houston , 4800 Calhoun Road, Houston, Texas 77204-5003, United States.
authors.forename: Han Ju
authors.initials: HJ
authors.lastname: Lee
authors.affiliation: Department of Chemistry and the Texas Center for Superconductivity, University of Houston , 4800 Calhoun Road, Houston, Texas 77204-5003, United States.
authors.forename: Andrew C
authors.initials: AC
authors.lastname: Jamison
authors.affiliation: Department of Chemistry and the Texas Center for Superconductivity, University of Houston , 4800 Calhoun Road, Houston, Texas 77204-5003, United States.
authors.forename: T Randall
authors.initials: TR
authors.lastname: Lee