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Corresponding Author(s)

徐龙华（1988—），女，山东农业大学副教授，博士。E-mail：[email protected]

Abstract

[Objective] To establish a surface -enhanced Raman scattering (SERS ) sensing method based on AuPt bimetallic nanozymes for the detection of thiamethoxam (TMX ) residues in agricultural products. [Methods] SiO2-supported AuPt bimetallic nanozymes were prepared using a reduction method. The excellent peroxidase -like activity of the nanozymes was utilized to catalyze the oxidation of 3,3', 5,5'-tetramethylbenzidine (TMB ) by H2O2 to generate oxidized TMB (ox-TMB ). The Raman signal of ox -TMB was enhanced by the localized surface plasmon resonance effect of the AuPt bimetallic nanostructure. Based on the inhibitory effect of TMX on acetylcholinesterase (AChE ) activity, the generation amount of ox -TMB in the system was regulated, and quantitative analysis of TMX was achieved by measuring the intensity of the characteristic peak at 1 607 cm-1. [Results] The prepared AuPt bimetallic nanozymes exhibited good morphology, stability, and catalytic activity. Under optimal conditions, the TMX concentration showed a good linear relationship with the SERS characteristic peak intensity at 1 607 cm-1 within the range of 0.1~100.0 μg/L (R2=0.994 9). The limit of detection was 0.066 μg/L. The recoveries of spiked actual samples ranged from 96.0% to 103.6%, with relative standard deviations of 3.0%~4.4%. [Conclusion] The developed SERS sensing platform exhibited good sensitivity, stability, anti -interference capability, and practical application potential.

Publication Date

11-3-2026

First Page

63

Last Page

72

DOI

10.13652/j.spjx.1003.5788.2026.80542

References

[1] Bai M,Chai Y Z,Chen A W,et al.Co-Mn-Fe spinel-carbon composite catalysts enhanced persulfate activation for degradation of neonicotinoid insecticides:(Non) radical path identification,degradation pathway and toxicity analysis [J].Journal of Hazardous Materials,2023,460:132473.

[2] Klingelhöfer D,Braun M,Brüggmann D,et al.Neonicotinoids:a critical assessment of the global research landscape of the most extensively used insecticide [J].Environmental Research,2022,213:113727.

[3] 高猛峰,童金蓉,梅博,等.超高效液相色谱—串联质谱法测定生牛乳中 10种新烟碱类农药残留 [J].食品与机械,2025,41(1):74-79.Gao M F,Tong J R,Mei B,et al.Simultaneous determination of 10 neonicotinoid pesticides in raw milk by ultra-high performance liquid chromatography tandem mass spectrometry[J].Food & Machinery,2025,41(1):74-79.

[4] Liu S D,Wei H R.Enhanced ligand exchange for ultrasensitive neonicotinoid detection in soil water via surface-enhanced Raman spectroscopy [J].Water Research,2025,286:124268.

[5] Tian F J,Qiao C K,Wang C X,et al.The fate of thiamethoxam and its main metabolite clothianidin in peaches and the wine-making process [J].Food Chemistry,2022,382:132291.

[6] Campanale C,Massarelli C,Losacco D,et al.The monitoring of pesticides in water matrices and the analytical criticalities:a review [J].TrAC Trends in Analytical Chemistry,2021,144:116423.[7] Ma L Y,Wan Q,Ge J,et al.Growth-promoting bacterium Enterobacter sp.CS8-gfp triggers jasmonate signaling pathway for atrazine and thiamethoxam degradation in rice (Oryza sativa L.) [J].Journal of Cleaner Production,2025,522:146373.

[8] Zhu S Y,Zhang J L,Chen A W,et al.Newly discovered cyanobacteria Nostoc sp.PCC 7120 for high efficiency biodegradation of thiamethoxam:photosynthesis response,enzyme strategies,and molecular mechanisms [J].Bioresource Technology,2025,436:132979.

[9] Naumann T,Bento C P M,Wittmann A,et al.Occurrence and ecological risk assessment of neonicotinoids and related insecticides in the Bohai Sea and its surrounding rivers,China[J].Water Research,2022,209:117912.

[10] Shi J L,Wang X L,Chen Z Y,et al.Spatial distribution of two acaricides and five neonicotinoids in beehives and surrounding environments in China [J].Journal of Hazardous Materials,2024,469:133892.

[11] Wang H J,Zhan J H,Gao L W,et al.Kinetics and mechanism of thiamethoxam abatement by ozonation and ozone-based advanced oxidation processes [J].Journal of Hazardous Materials,2020,390:122180.

[12] Zhang J G,Ma D D,Li S Y,et al.A time-course transcriptional kinetics of genes in behavior,cortisol synthesis and neurodevelopment in zebrafish larvae exposed to imidacloprid and thiamethoxam [J].Bulletin of Environmental Contamination and Toxicology,2022,110(1):5.

[13] Selahle S K,Mpupa A,Nomngongo P N.Combination of zeolitic imidazolate framework- 67 and magnetic porous porphyrin organic polymer for preconcentration of neonicotinoid insecticides in river water [J].Journal of Chromatography A,2022,1 661:462685.

[14] 杨艳梅,李晋栋,秦曙.QuEChERS/ 超高效液相色谱—串联质谱法同时检测土壤中的农药及抗生素残留 [J].分析测试学报,2023,42(7):808-816.Yang Y M,Li J D,Qin S.Simultaneous detection of pesticides and antibiotics residues in soil by QuEChERS/ultra performance liquid chromatography-tandem mass spectrometry[J].Journal of Instrumental Analysis,2023,42(7):808-816.

[15] 李欣,李帮锐,陈东洋,等.固相萃取—超高效液相色谱—串联质谱法测定葡萄酒中 12种合成色素 [J].食品与机械,2026,42(3):49-56.Li X,Li B R,Chen D Y,et al.Determination of 12 synthetic pigments in wine by solid phase extraction with ultra-high performance liquid chromatography-tandem mass spectrometry[J].Food & Machinery,2026,42(3):49-56.

[16] Yang B X,Tu M L,Wang S,et al.Neonicotinoid insecticides in plant-derived Foodstuffs:a review of separation and determination methods based on liquid chromatography [J].Food Chemistry,2024,444:138695.

[17] 王宁,粟有志,雷红琴,等.全自动固相萃取—高效液相色谱—串联质谱法测定水中 150种农药残留 [J].分析科学学报,2023,39(3):309-318.Wang N,Su Y Z,Lei H Q,et al.Determination of 150 pesticides residues in water by automated solid phase extraction coupled with HPLC-MS/MS [J].Journal of Analytical Science,2023,39(3):309-318.

[18] Watanabe E.Review of sample preparation methods for chromatographic analysis of neonicotinoids in agricultural and environmental matrices:from classical to state-of-the-art methods [J].Journal of Chromatography A,2021,1 643:462042.

[19] Wang W R,Wang X X,Cheng N,et al.Recent advances in nanomaterials-based electrochemical (bio)sensors for pesticides detection [J].TrAC Trends in Analytical Chemistry,2020,132:116041.

[20] Kneipp J,Kneipp K.Surface enhanced nonlinear Raman processes for advanced vibrational probing [J].ACS Nano,2024,18(32):20 851-20 860.

[21] Magdy M.A conceptual overview of surface-enhanced Raman scattering (SERS ) [J].Plasmonics,2023,18(2):803-809.

[22] 杨海帆,丁莉,徐妙文,等.QuEChERs 方法结合 SERS技术检测猪肉中氨基糖苷类抗生素残留 [J].食品与机械,2024,40(3):68-74,81.Yang H F,Ding L,Xu M W,et al.Detection of aminoglycoside antibiotic residues in pork by QuEChERs method combined with SERS technique [J].Food & Machinery,2024,40(3):68-74,81.

[23] Wang P X,Lin H,Cao L M,et al.Recent advances in SERS hotspot regulatory strategies and their applications in food safety detection [J].Food Chemistry,2025,495:146488.

[24] Wang T,Wei J,Cheng Z,et al.Plasmonic nanocubes with a controllable "crescent arc" facet:tunable hotspot engineering for highly reliable and sensitive SERS detection [J].Analytical Chemistry,2024,96(43):17 453-17 462.

[25] 王留留,孙方涛.表面增强拉曼光谱技术在食品安全检测领域中的应用 [J].食品与机械,2024,40(1):212-218.Wang L L,Sun F T.Application of surface-enhanced Raman spectroscopy in food safety detection [J].Food & Machinery,2024,40(1):212-218.

[26] 王悦,李晓东,张瑞,等.表面增强拉曼散射基底增强机制及其在痕量检测中的研究进展 [J].分析测试学报,2024,43(2):215-226.Wang Y,Li X D,Zhang R,et al.Research progress on enhancement mechanisms of surface-enhanced Raman scattering substrates and their applications in trace detection[J].Journal of Instrumental Analysis,2024,43(2):215-226.

[27] Tadanaga K,Morita K,Mori K,et al.Synthesis of monodispersed silica nanoparticles with high concentration by the Stöber process [J].Journal of Sol-Gel Science and Technology,2013,68(2):341-345.

[28] Ma Z Y,Wu L,Han K,et al.Pt nanozyme for O2 self-sufficient,tumor-specific oxidative damage and drug resistance reversal [J].Nanoscale Horizons,2019,4(5):1 124-1 131.

[29] 李春颖,王红义,陈高乐,等.表面增强拉曼光谱法在动物源性食品安全检测中的应用 [J].食品工业科技,2023,44(16):434-443.Li C Y,Wang H Y,Chen G L,et al.Application of surface-enhanced Raman spectroscopy in animal derived foods safety[J].Science and Technology of Food Industry,2023,44(16):434-443.

[30] 林丙永,王悦靓,林振宇,等.基于贵金属纳米复合材料的表面增强拉曼散射活性基底的构建及其应用进展 [J].分析化学,2022,50(5):653-665.Lin B Y,Wang Y L,Lin Z Y,et al.Fabrication and application of noble metal nanocomposites-based surface-enhanced Raman scattering active substrate [J].Chinese Journal of Analytical Chemistry,2022,50(5):653-665.

[31] 郭春梅,尹维翰,石静怡,等.单原子铂纳米酶的简便构建及其类过氧化物酶活性 [J].无机化学学报,2024,40(9):1 633-1 639.Guo C M,Yin W H,Shi J Y,et al.Facile construction and peroxidase-like activity of single-atom platinum nanozyme [J].Chinese Journal of Inorganic Chemistry,2024,40(9):1 633-1 639.

[32] 彭邹君,邱萍.基于乙酰胆碱酯酶抑制的有机磷农药生物传感器研究进展 [J].分析测试学报,2022,41(3):426-434.Peng Z J,Qiu P.A review of organophosphorus pesticide biosensors based on acetylcholinesterase inhibition [J].Journal of Instrumental Analysis,2022,41(3):426-434.

[33] Mohamed S A,Abdel-Aty A M,Al-Talhi H A,et al.The patterns of acetylcholinesterases during developmental stages of Aedes aegypti and their susceptibility toward insecticides in egg stage [J].Scientific Reports,2026,16:12730.

[34] Gao L Z,Zhuang J,Nie L,et al.Intrinsic peroxidase-like activity of ferromagnetic nanoparticles [J].Nature Nanotechnology,2007,2(9):577-583.

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