Sensitive Detection of Polycyclic Aromatic Molecules: Surface Enhanced Raman Scattering via π-π Stacking.

We report silver nanoparticles (Ag NPs) with high stability, sensitivity, and no surface enhanced Raman scattering (SERS) background. The Ag NPs were synthesized via a one-step process with polysodium styrenesulfonate (PSSS) templates, and they could efficiently adsorb polycyclic aromatic molecules via π-π stacking. The adsorption mechanisms and applicability were systematically studied by experimental measurements and theoretical simulations. When the polycyclic aromatic analytes were adsorbed on the PSSS-templated Ag NPs, the vibrations of π-π stacking-bound moieties were attenuated, yet those of the other unbound aromatic moieties increased. Most importantly, when the analytes had more than two π-π stacking binding sites, the PSSS-templated Ag NPs could trap the analytes by focusing through the optical force induced or via the simultaneously formed analyte-Ag NPs aggregates. This afforded high SERS intensity and very low detection limits.