ABSTRACTMetal nanoparticles are of great importance in the fabrication of new nanocomposite materials. One area of increasing interest is the application of metal nanoparticles (NP) as substrates for surface enhanced Raman scattering (SERS). In this regard, self-assembled monolayers (SAMs) of sulfur containing organic compounds are ideal target for SERS studies due to the strong affinity of sulfur for noble metals. Two types of molecules were synthesized for this study, an organic-soluble and a water-soluble styrene derivative. Self-assembling behaviors of these monomers on gold or silver nanostructured surfaces at room temperature were studied by UV-Vis spectroscopy, dynamic light scattering (DLS), SERS spectroscopy, and scanning electron microscopy (SEM). It was found that the interaction between sulfur compounds and metal NPs is strongly dependent on the NP size and the monomer environment. The hydrophilic NP surface switches to hydrophobic upon binding of sulfur-containing monomers, which leads to the formation of aggregates in aqueous solution for both water-soluble and oil-soluble monomers. The self-assembling behavior of these monomers on the metallic surface was compared with that of the corresponding homopolymers. Due to macromolecular and steric effects, the binding interaction between homopolymer and metal NP is weaker than that between NP and monomers. Surface polymerization of these monomers on metallic surfaces was observed as supported by SERS. Core-shell nanoparticles could also be obtained through seeded emulsion polymerization, but a decrease in SERS activity was observed.
Using Polystyrene-block-poly(acrylic acid)-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization