Chemometrics coupled 4-Aminothiophenol labelled Ag-Au alloy SERS off-signal nanosensor for quantitative detection of mercury in black tea.

Black tea like other food crops is prone to mercury ion (Hg2+) contamination right from cultivation to industrial processing. Due to the dangerous health effects posed even in trace contents, sensitive detection and quantification sensors are required. This study employed the surface-enhanced Raman scattering (SERS) enhancement property of 4-aminothiophenol (4-ATP) as a signal turn off approach functionalized on Ag-Au alloyed nanoparticle to firstly detect Hg2+ in standard solutions and spiked tea samples. Different chemometric algorithms were applied on the acquired SERS and inductively coupled plasma-mass spectrometry (ICP-MS) chemical reference data to select effective wavelengths and spectral variables in order to develop models to predict the Hg2+. Results indicated that Ag-Au/4-ATP SERS sensor combined with ant colony optimization partial least squares (ACO-PLS) exhibited the best correlation efficient and minimum errors for Hg2+ standard solutions (Rc = 0.984, Rp = 0.974, RMSEC = 0.157 μg/mL, RMSEP = 0.211 μg/mL) and spiked tea samples (Rc = 0.979, Rp = 0.963, RMSEC = 0.181 μg/g and RMSEP = 0.210 μg/g). The limit of detection of the proposed sensor was 4.12 × 10-7 μg/mL for Hg2+ standard solutions and 2.83 × 10-5 μg/g for Hg2+ spiked tea samples. High stability and reproducibility with relative standard deviation of 1.14% and 0.84% were detected. The potent strong relationship between the SERS sensor and the chemical reference method encourages the application of the developed chemometrics coupled SERS system for future monitoring and evaluation of Hg2+ in tea.