CoFe2O4@HNTs/AuNPs Substrate for Rapid Magnetic Solid-Phase Extraction and Efficient SERS Detection of Complex Samples All-in-One

Fast and accurate practical sample detection is a great challenge in on-site detection. Herein, we developed a CoFe2O4@HNTs/AuNPs substrate for rapid and efficient magnetic solid-phase extraction (MSPE) surface-enhanced Raman scattering (SERS) detection of aromatic amines and nitrofuran in real samples all-in-one. Magnetic CoFe2O4 beads filled inside halloysite nanotubes (HNTs) can avoid aggregation of particles, endow the substrate with the rapid magnetic separation ability to simplify the pretreatment procedure, and reduce complex matrix interference. Meanwhile, outer surface AuNPs can generate electromagnetic enhancement and hot spots to amplify Raman signals of target molecules enriched/concentrated by HNTs. The CoFe2O4@HNTs/AuNPs substrate exhibited excellent SERS activity (high sensitivity, good reproducibility, and repeatability), pH stability (3.0–11.0), and good MSPE ability (fast magnetic enrichment/separation ability within 5 min). The CoFe2O4@HNTs/AuNPs MSPE SERS substrate can be applied for the determination of 4,4′-thioaniline and nitrofurantoin with a linear range of 0.054–21.7 mg/L and 0.05–1.0 mg/L, and the limits of detection were down to 0.026 mg/L and 0.014 mg/L, respectively. Furthermore, the enhancement factor (EF) of the substrate to 4,4′-thioaniline is up to 2.7 × 107. Besides, the substrate can realize practical SERS determination of trace 4,4-thioaniline in cosmetics and nitrofurantoin in fish feed and aquatic samples. The recoveries were varied from 71.6% to 103.6% for 4,4-thioaniline in hair dyes and 81.9% to 116.3% for nitrofurantoin in fish feed and aquatic samples, respectively. Such a robust and efficient MSPE SERS substrate possesses great potential in rapid detection (within 15 min) for a practical sample, and it also provides a methodology for the preparation of other HNTs-based composites.