There is a need to design highly sensitive plasmonic sensors which impart a good biocompatibility and optical stability to detect low levels of analytes in biological media. In this study we report the formation of chitosan-coated silver nanoparticles of triangular shape in solution by synergistic action of chitosan and trisodium citrate in the presence of silver seeds and ascorbic acid. It has been revealed that these anisotropic silver nanoparticles entrapped in biopolymeric shells are particularly stable and can be successfully used as versatile plasmonic substrates for molecular sensing in solution. In particular, the binding of the probe molecule monolayer (para-aminothiophenol, p-ATP) at the surface of individual chitosan-coated silver nanoparticles was demonstrated both by localized surface plasmon resonance (LSPR) shifts and surface-enhanced Raman scattering (SERS) spectra. While the LSPR-shift assay is operational for signaling molecular binding events, the SERS allows identifying the probe molecules and elucidating its orientation on the metal surface. The proof of concept for biosensing applications and dual functionality of plasmonic platform are evaluated through the combined LSPR-SERS detection of significant biological molecules, adenine. The potential of chitosan–silver nanostructures to extend the standard approach of LSPR sensing by integrating SERS measurements and operate as dual plasmonic sensors would be very attractive for investigation of analytes in biological fluids.
A new green method for the synthesis of reduced graphene oxide–gold nanoparticle (rGO–AuNP) hybrids in aqueous solution that exploits the ability of ascorbic acid (AA) to operate as an effective dual agent for both graphene oxide (GO) and gold ion reduction is reported. Through careful investigation of the production of rGO–AuNP hybrids stabilized with polyvinylpyrrolidone (PVP), several versatile routes were devised with the aim of controlling the size, shape and distribution of AuNPs anchored onto the graphene sheets as well as the GO reduction. Particularly, when rGO is used as a platform for Au ion nucleation, a relative sparse distribution of AuNPs of size ranging from 20 nm to 50 nm is noticed. In contrast, when gold ions are added to the solution prior to any GO reduction, the density of large AuNPs is rather low relative to the uniformly packed small sized AuNPs (3–12 nm). The progress of GO reduction is explained by considering the contribution of the catalytic activity of AuNPs, besides the reducing activity of AA. Finally, a plausible mechanism for the nucleation and distribution of AuNPs onto the graphenic surface is assumed, highlighting the significance of oxygen moieties. The green method developed here is promising for the fabrication of gold–graphene nanocomposites with tunable surface “decoration”, suitable for surface-enhanced Raman spectroscopy (SERS).
24 May 2012 in The Journal of Physical Chemistry C