Self-Cleaning-Mediated SERS Chip Coupled Chemometric Algorithms for Detection and Photocatalytic Degradation of Pesticides in Food

Abstract

Pesticide residues in food have been a grave concern to consumers. Herein, we have developed a dual-mode SERS chip using Cu 2 O mesoporous spheres decorated with Ag nanoparticles (MCu 2 O@Ag NPs) as both sensing and degradation/ clearing unit for rapid detection of pymetrozine and thiram pesticides in tea samples. Three kinds of chemometric algorithms were comparatively applied to analyze the collected SERS spectra of pesticides. In comparison, random frog-partial least squares achieved the best performance with root mean square error of prediction and residual predictive deviation values of 0.9871, 6.17, and 0.9873, 6.64 for pymetrozine and thiram, respectively. Additionally, the prepared SERS chip showed great photocatalytic activity to degrade pesticides under visible light irradiation. Through a facile method, this work presented a novel dual-functional SERS chip for the rapid detection and degradation of low-concentration pesticides in both environmental and food samples.

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.…”

“…River water and apple juice 9.58 nM [203] Gold nanoparticles Imidacloprid Analyte and SERS substrate - [204] Gold-gel Parathion-methyl Analyte on SERS substrate 10 -9 M [199] Silver nanoparticles Pymetrozine Apple and cabbage 0.01 mg/L [214] Silver @ DNA/PDA-cellulose nanofiber Thiamethoxam Apple 0.003 mg/kg [59] Mesoporous copper (I) oxide @ silver nanoparticles Pymetrozine and thiram Tea 0.1 ng/g [160] Gold substrate Acetamiprid and imidacloprid Plasmon activated water 5 and 10 μg/L [205] Ag@D-TMIP Carbaryl and thiodicarb Spiked tap water - [208] Silver Gold nanostars / PDMS Methyl parathion Apple 1.946 μg/mL [198] Gold @ silver nanorods Nile blue A dye and fenobucarb pesticide Analyte on SERS substrate 1.5 × 10 −8 M (fenobucarb) [213] Articles were obtained by performing the following search on Web of Science and removing non-environmental papers: SERS + Pesticide. The table details substrate type, analyte type, the sample or sample matrix used, method LOD and the corresponding reference.…”

“…While the toxicity of most fungicides is generally low, prolonged exposure to these compounds may lead to adverse health effects such as neurological disruptions 126 . Several recent studies have utilized SERS to detect various fungicides, including tetramethylthiuram disulfide (THR), 39,53,61,70,79,127–161 carbendazim, 162–165 chlorothalonil, 166,167 MG, 168–173 TBZ (a fungicide and parasiticide) 20,79,153,155,173–178 and ferbam 20,178,179 . Among them, THR is the most studied due to its wide agricultural applications and strong binding with SERS nanosubstrates through the thiol group.…”

Large-area and low-cost SERS substrates based on a gold-coated nanostructured surface fabricated on a wafer-scale

“…SERS has been used for the detection of various pesticides. 38,39 The use of organophosphorous pesticidesparaoxon ethyl and paraoxon methyl are even banned in certain regions due to concerns regarding exposure and potential impact on non-target organisms. Hence, specic detection of the presence of pesticides in drinking and human-use water is very important so that animal and human health risks can be avoided.…”

Investigation of the adsorption of pymetrozine on the Au@AgNPs surface and its application in the rapid detection of pymetrozine residues in apple

“…Pymetrozine ((E)-4,5-dihydro-6-methyl-4-(3-pyridylmethyleneamino)-1,2,4-triazin-3(2H)-one) is a pyridine azomethine compound, which has four pK a values (pK a1 = 12.90, pK a2 = 3.71, pK a3 = 1.82, and pK a4 = −3.92) controlling the relative population of deprotonated, neutral and protonated forms in solution based on the pH value. Recently, multitudinous studies have been reported on the SERS detection of pymetrozine residues, which focused on complex solid SERS substrates and dry-prepared pymetrozine samples ( Shen et al, 2021 , Xu et al, 2021 , Xu et al, 2020 ). However, few test methods are available for pymetrozine detection by samples with wet preparation, and up to now the adsorption behavior of pymetrozine on SERS substrate surface has not been studied.…”