Ultrasensitive SERS Detection of Five β‑Blockers Achieved Using Chemometrics with a Two-Dimensional Substrate Formed by Large-Sized Ag@SiO2 Nanoparticles

We report on a surface-enhanced Raman scattering (SERS) platform for the detection of five beta-blockers (β-blockers): atenolol, esmolol, labetalol, sotalol, and propranolol. Key to this platform was a two-dimensional substrate formed by self-assembling large Ag@SiO2 nanoparticles (Ag@SiO2 NPs) on a silicon wafer. The close arrangement of these large nanoparticles on the surface generated a strong and uniform electromagnetic field, which enhanced SERS signal intensity for the detection of small amounts of the target molecules. The intensities of characteristic peaks of the five β-blocker drugs increased linearly with the increase of their concentrations in the range of 10–5 to 10–8 mol/L. The detection limits were 10–10 mol/L for propranolol, 10–9 mol/L for atenolol, labetalol, and sotalol, and 10–8 mol/L for esmolol. Determination of these five β-blocker drugs added to human urine samples, using a portable Raman spectroscopy instrument, showed quantitative recovery (93–101%). Principal component analysis (PCA) and hierarchical cluster analysis (HCA) of SERS spectral data improved the differentiation among these five β-blockers. This study highlights the potential of the developed SERS platform for rapid, on-site detection of illicit drugs and for antidoping screening.