Combining surface-accessible Ag and Au colloidal nanomaterials with SERS for in situ analysis of molecule-metal interactions in complex solution environments

The interactions between molecules and noble metal nanosurfaces play a central role in many areas of nanotechnology. The surface chemistry of noble metal surfaces under ideal, clean conditions has been extensively studied; however, clean conditions are seldom met in real-world applications. We developed a sensitive and robust characterization technique for probing the surface chemistry of nanomaterials in the complex environments that are directly relevant to their applications. Surface-enhanced Raman spectroscopy (SERS) can be used to probe the interaction of plasmonic nanoparticles with light to enhance the Raman signals of molecules near the surface of nanoparticles. Here, we explain how to couple SERS with surface-accessible plasmonic-enhancing substrates, which are capped with weakly adsorbing capping ligands such as citrate and chloride ions, to allow molecule-metal interactions to be probed in situ and in real time, thus providing information on the surface orientation and the formation and breaking of chemical bonds. The procedure covers the synthesis and characterization of surface-accessible colloids, the preliminary SERS screening with agglomerated colloids, the synthesis and characterization of interfacial nanoparticle assemblies, termed metal liquid-like films, and the in situ biphasic SERS analysis with metal liquid-like films. The applications of the approach are illustrated using two examples: the probing of pi-metal interactions and that of target/ligand-particle interactions on hollow bimetallic nanostars. This protocol, from the initial synthesis of the surface-accessible plasmonic nanoparticles to the final in situ biphasic SERS analysis, requires similar to 14 h and is ideally suited to users with basic knowledge in performing Raman spectroscopy and wet synthesis of metal nanoparticles.

Automated summary

This article presents a sensitive and robust characterization technique, SERS, for studying the surface chemistry of nanomaterials in real-world applications. It allows real-time observation of molecule-metal interactions and provides information on surface orientation and chemical bond formation and breaking.