Au Sputtered Paper Chromatography Tandem Raman Platform for Sensitive Detection of Heavy Metal Ions

Surface-enhanced Raman scattering (SERS) is a powerful technique for sensitive detection, but it normally has difficulty in multicomponent detection in a complex system, especially for simultaneous analysis of mixture of heavy metal ions. In this work, a simple paper chromatography tandem SERS (PC-SERS) separation/detection platform is proposed by ion-sputtering gold on a filter paper. Based on SEM results, the great electromagnetic field inside nanogaps of Au nanoislands on the paper surface is evaluated with FDTD simulation. It is found that the PC-SERS platform has good uniformity (RSD = 10.12%) and long-time stability. The as-prepared PC-SERS platform was applied to efficiently separate and detect a mixture of pesticides (MG, MB, and CV) in pond water without any pretreatment process, and the limits of detection (LODs) were down to 10 nM. As a crucial application for food safety, several heavy metal ions such as Cd²⁺, Cu²⁺, and Ni²⁺ in grinded rice were successfully detected by the PC-SERS method taking advantage of the sandwich structure based on 4-mercaptobenzoic acid (4-MBA) molecules, which were modified onto sputtering the Au filter paper and gold nanoparticles (Au NPs) to link metal ions and acted as Raman signal molecules. All the LODs for metal ions were down to 1 μM. Due to the easiness of fabrication, good reproducibility, and simple pretreatment step, the PC-SERS platform holds promise in multicomponent detection in a real sample.