Optimizing Au/Ag core–shell nanorods: purification, stability, and surface modification

The purification, stability, and surface modification of Au/Ag core–shell nanorods (Au/Ag NRs) in a biological buffer solution were systematically studied for the first time. In this study, Au/Ag NRs were synthesized by chemically reducing silver on the surface of gold nanorods using cetyltrimethylammonium bromide as surfactant and then purified by centrifugation washing. Based on the analysis of UV–Vis absorption spectra, TEM images, Raman spectra, and the ξ-potential, it was observed that after the second washing step, the Au/Ag NRs displayed good stability and high surface-enhanced Raman scattering (SERS) enhancement. When the as-prepared Au/Ag NRs were centrifuged more than twice, a structural transition in the surfactant layer was manifested with a sudden increase in the Raman signal intensities at 760 and 1,455 cm−1. Moreover, 4-mercaptobenzoic acid (4MBA) was used as a Raman reporter molecule to investigate the SERS characteristics of the purified Au/Ag NRs. The Raman signal intensity was enhanced with increasing the concentration of 4MBA and reached its highest intensity at the saturation concentration of 1.0 µM 4MBA in a 5 ml solution of the purified Au/Ag NRs. To prevent significant aggregation of the 4MBA-tagged Au/Ag NRs, a poly(styrenesulfonate) (PSS) layer was assembled on the nanorod surfaces by electrostatic adsorption for further surface modification, which made the 4MBA-tagged Au/Ag NRs suitable for the labeled biosensing. Subsequently, the characteristics of the PSS-coated Au/Ag NRs were demonstrated for the potential applications of label-free biosensing.