Gap-Tethered Au@AgAu Raman Tags for the Ratiometric Detection of MC-LR

Establishing a simple and accurate assay for detecting Microcystin-LR (MC-LR) is of significant important for the environment and human health. Herein, we develop a ratiometric surface-enhanced Raman scattering (SERS) aptasensor based on internal standard (IS) methods for the sensitive and reproducible quantitative detection of MC-LR. Gap-tethered SERS-active Au@AgAu nanoparticles (NPs) are successfully prepared and the gap sizes are adjustable by simply adjusting the acidity. Gap-tethered Au@AgAu NPs exhibit gap-tunable amplified SERS activity and are served as SERS tags. The graphene oxide (GO)/Fe₃O₄ NPs demonstrate a unique and stable Raman band from the graphitic component, making them an ideal IS for quantitative Raman analysis. In principle, Au@gap@AgAu NPs are assembled with GO/Fe₃O₄ NPs depending on the π-π stacking interaction between GO and MC-LR aptamers. In the presence of MC-LR, Au@gap@AgAu NPs are dissociated from GO/Fe₃O₄ NPs due to the affinity of aptamer, leading to the changes of Raman intensity of SERS tags. Quantitatively, upon correction by the IS Raman signals, the limit of detection (LOD) is as low as 9.82 pM for MC-LR. The developed protocol provides a simple and rapid approach for the sensitive and quantitative detection of MC-LR and shows great promise for applications in complex systems.