Facile Detection and Quantification of Acetamiprid Using a Portable Raman Spectrometer Combined with Self-Assembled Gold Nanoparticle Array

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).

Irradiation-Induced Synthesis of Ag/ZnO Nanostructures as Surface-Enhanced Raman Scattering Sensors for Sensitive Detection of the Pesticide Acetamiprid

“…Upon adding the acetamiprid solution, the Ag particle distance decreases owing to the absorption of acetamiprid molecules and the resonance spots for the acetamiprid SERS spectra. The EF value increased from 1000 to 2.95 × 10 7 M as the concentration of DPY diminished from 4.5 × 10 −4 M to 4.5 × 10 −7 M. The limit of detection of acetamiprid using the SERS technique was determined to be 4.5 × 10 −7 M, which is lower by a factor of seven than the optimum levels specified by the U.S. EPA in drinking water and is comparable to the examination capability reported in previous studies [45][46][47].…”

Applications of surface‐enhanced Raman spectroscopy in environmental detection

“…Insecticides are used to kill or repel insects and are often used in agricultural settings to protect crops from destruction. SERS has been used to detect several types of insecticides in the past year such as chlorpyrifos, 159,[194][195][196][197] methyl parathion, 151,[198][199][200] endosulfan, 155,201 malathion, 155 phosmet, 156 imidacloprid, 159,167,191,[202][203][204][205][206][207] phorate, 157 carbaryl, 158,208 fipronil, 158 fenitrothion, 193 acetamiprid, 165,192,205,206,209 chlorfenapyr, 210 dichlorvos, 211,212 fenobucarb, 213 thiodicarb, 208 carbendazim, 165 profenofos, 165 methomyl, 192 pymetrozine, 160,214 clothianidin and thiamethoxam. 59,206 Recently, Sulaiman et al created a technique for the sensitive detection of the insecticide chlorpyrifos using fabricated bi-metallic nanoparticle alloys in conjunction with SERS.…”

Rapid Detection of Malathion, Phoxim and Thiram on Orange Surfaces Using Ag Nanoparticle Modified PDMS as Surface-Enhanced Raman Spectroscopy Substrate

“…In order to achieve rapid and on-site screening for these pesticides, many analytical methods have been developed in recent years, including electrochemical sensors [ 16 , 17 ], enzymatic inhibition-based sensors [ 18 ], enzyme-linked immunosorbent assay (ELISA) [ 19 ], lateral flow strip [ 20 ], surface-enhanced Raman spectroscopy (SERS) [ 21 ], microfluidics [ 22 ], and so forth. Among them, in recent decades SERS has been developed as a promising analytical platform for rapid and on-site detection of various target molecules [ 23 , 24 ]. Highly sensitive SERS detection depends on the enhancement of the Raman scattering signal generated from the localized surface plasmon resonance (LSPR) effect of Au or Ag nanomaterials.…”