Abstract

Rapid and facile determination of pesticides is critically important in food and environmental monitoring. This study developed a self-assembled gold nanoparticle array based SERS method for highly specific and sensitive detection of acetamiprid, a neonicotinoid pesticide that used to be difficult in SERS analysis due to its low affinity with SERS substrates. SERS detection and quantification of acetamiprid was conducted with self-assembled gold nanoparticle arrays at the interface of chloroform and water as the enhancing substrate. Since targets dissolved in chloroform (organic phase) also have access to the hot-spots of Au NP array, the developed method exhibited good sensitivity and specificity for acetamiprid determination. Under the optimal conditions, SERS intensities at Raman shifts of 631 cm−1 and 1109 cm−1 displayed a good linear relationship with the logarithm concentration of acetamiprid in the range of 5.0 × 10−7 to 1.0 × 10−4 mol/L (0.11335 ppm to 22.67 ppm), with correlation coefficients of 0.97972 and 0.97552, respectively. The calculated LOD and LOQ of this method were 1.19 × 10−7 mol/L (0.265 ppb) and 2.63 × 10−7 mol/L (0.586 ppb), respectively, using SERS signal at 631 cm−1, and 2.95 × 10−7 mol/L (0.657 ppb) and 3.86 × 10−7 mol/L (0.860 ppb) using SERS signal at 1109 cm−1, respectively. Furthermore, the developed SERS method was successfully applied in determining acetamiprid on the surface of apple and spinach. This method offers an exciting opportunity for rapid detection of acetamiprid and other organic pesticides considering its advantages of simple preparation process, good specificity and sensitivity, and short detection time (within 1 h).

Highlights

  • Au NPs were synthesized by a citrate reduction method and characterized with UV-Vis spectroscopy, particle size analyzer, and transmission electron microscopy (TEM)

  • Au NPs exhibited good optical property depending on their localized surface plasmon resonance (LSPR) bands [23]

  • Acetamiprid, clothianidin, imidacloprid, and thiamethoxam all belong to neonicotinoid pesticides and were selected to assess the specificity of the developed Surface-enhanced Raman scattering (SERS) method

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Summary

Introduction

Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. Chemosensors 2021, 9, 327 liquid/gas chromatography tandem mass spectrometry (LC-MS/GC-MS) [12] These methods possess good specificity and accuracy, these methods depend on complex sample preparation procedures, expensive instruments, and professional personnel [13]. Their applications in the rapid detection of acetamiprid have been hindered by these shortcomings. Surface-enhanced Raman scattering (SERS) is a combination of Raman scattering and nanotechnology It has advantages of simple sample preparation, rapid response, high sensitivity, and simultaneous characterization capacity [14]. We proposed a facile and rapid SERS method for the detection and quantification of acetamiprid using a self-assembled Au NP array at the interface of water and chloroform as the enhancing substrate.

Reagents and Instruments
Synthesis of Au NP Colloid
SERS Detection of Acetamiprid
Real Sample Detection
Results and Discussion
Optimization
Specificity of the Developed Self-Assembled Au NP Array Based SERS Method
Conclusions
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