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Robust Maleimide-Functionalized Gold Surfaces and Nanoparticles Generated Using Custom-Designed Bidentate Adsorbates.

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Custom alkanethioacetate ligands enable robust attachment of molecules to gold nanostructures. Ligands with oligo(ethylene glycol) (OEG) and chelating dithioacetate groups enhance nanoparticle stability in solution and resist displacement.

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Area of Science:

  • Materials Science
  • Surface Chemistry
  • Nanotechnology

Background:

  • Developing stable gold nanostructures requires effective surface modification techniques.
  • Controlling the attachment and stability of adsorbates on gold surfaces is crucial for various applications.

Purpose of the Study:

  • To synthesize custom alkanethioacetate ligands for facile attachment of maleimide-terminated adsorbates to gold nanostructures.
  • To investigate the influence of ligand structure, including oligo(ethylene glycol) (OEG) moieties and dithioacetate groups, on monolayer formation and gold nanoparticle (AuNP) stability.

Main Methods:

  • Synthesis of mono- and dithioacetate ligands with varying alkyl spacers and OEG content.
  • Characterization of monolayers on gold substrates using X-ray photoelectron spectroscopy, FTIR-reflection-absorption spectroscopy, ellipsometry, and contact angle goniometry.
  • Preparation and stability assessment of gold nanoparticles (AuNPs) under extreme conditions (high salt, ligand exchange) using visual and spectroscopic methods.

Main Results:

  • Monolayer formation was solvent-dependent, with EtOH yielding higher packing density and THF providing better thiolate binding.
  • AuNPs functionalized with OEG-containing ligands showed enhanced colloidal stability in high salt concentrations.
  • AuNPs with dithioacetate ligands demonstrated improved resistance to ligand exchange, particularly against dithiothreitol (DTT).

Conclusions:

  • Chelating dithioacetate ligands incorporating OEG moieties provide the most effective combination of stability and solubility for gold nanostructures.
  • The chelate effect and OEG groups significantly enhance adsorbate attachment and colloidal stability in aqueous solutions.