Monolithic 3D structural-substrate SERS sensing platform for ultrasensitive and highly-specific analysis of trace...

Constructing advanced substrates with excellent features is promising for sensitive surface-enhanced Raman spectroscopy (SERS) detection. Here a novel capillary monolithic 3D structural-substrate SERS platform with Au@cDNA@Ag@Cyanine 3-aptamer nanoparticles (Au@cDNA@Ag@Cy3-Apt NPs) was fabricated for rapid, highly specific profiling of ultra-trace Bisphenol A (BPA). The proposed SERS platform combined both in-capillary SERS and aptamer-affinity recognition strategies, in which the superior SERS properties of Au-Ag NPs, aptamer selectivity, and the advantages of capillary monolith were integrated. A 3D hierarchically porous network was constructed in the monolithic column, which was endowed with rich hotspots for SERS, rapid sample permeation, and better analysis efficiency than most plane-shaped SERS modes. By varying the amount of Ag⁺ precursor, the Ag-shell thickness on SERS was finely tuned to guarantee Cy3 label in proximity to the plasmonic surface. Based on the biorecognition of aptamer, the selective identification of BPA occurred and exhibited a significant change in SERS intensity without obvious interference. As a result, the monolithic SERS platform featured facile operation, excellent specificity, and rapid analysis (10 min, much less than the solution-based or planar substrate SERS modes). Ultra-high sensitivity and robust reproducibility for BPA analysis was achieved with a low limit of detection (LOD) at 9.12 × 10^-4 ng/L. The feasibility of this SERS platform for monitoring BPA in water and milk samples was also validated. This work lights a new access to capillary monolithic SERS-sensing platform for ultrasensitive and specific analysis of BPA.