Ahmed Filayih Hassan (1)
General Background: Pesticide residues in food remain a global safety concern, requiring analytical methods that are both rapid and highly sensitive. Specific Background: Conventional chromatographic techniques provide accurate detection but are limited by high cost, long processing times, and complex sample preparation, restricting routine monitoring. Knowledge Gap: Despite growing interest in Surface-Enhanced Raman Scattering (SERS), challenges persist regarding substrate reproducibility, sensitivity across diverse food matrices, and validation against regulatory standards. Aims: This study aimed to develop, optimize, and validate nanostructured silver SERS substrates for the sensitive detection of organophosphorus and organochlorine pesticides in food. Results: The fabricated substrates achieved enhancement factors above 10⁸, detection limits as low as 0.05–0.1 ng/mL, strong linearity, high reproducibility, and accurate recovery across apple juice, tomato extract, and rice samples. Analytical performance showed strong agreement with GC-MS while reducing total analysis time to under 15 minutes. Novelty: The work integrates controlled nanoparticle aggregation with optimized sample-matrix handling, yielding highly reproducible, stable, and field-ready SERS substrates. Implications: The findings demonstrate a practical and cost-effective platform for high-throughput pesticide monitoring, with potential for portable on-site food safety assessment and future expansion to broader contaminant classes.Highlight :
Silver-based SERS substrates provide very high-sensitivity pesticide detection.
The method offers much faster analysis than conventional techniques.
It works effectively across multiple food matrices.
Keywords : SERS, silver nanoparticles, pesticide detection, food safety, surface enhancement, Raman spectroscopy
Sharma A., Kumar V., Shahzad B., et al., “Worldwide Pesticide Usage and Its Impacts on Ecosystem,” SN Applied Sciences, vol. 1, p. 1446, 2019.
Tang F. H. M., Lenzen M., McBratney A., dan Maggi F., “Risk of Pesticide Pollution at the Global Scale,” Nature Geoscience, vol. 14, pp. 206–210, 2021.
Food and Agriculture Organization (FAO), Pesticides Use, Pesticides Trade and Pesticides Indicators: Global, Regional and Country Trends 1990–2020, Rome: FAO, 2022.
Rajski Ł., Lozano A., Belmonte-Valles N., et al., “Determination of Pesticide Residues in High-Oil Vegetal Commodities Using Various Multiresidue Methods and Clean-Ups Followed by LC-MS/MS,” Journal of Chromatography A, vol. 1304, pp. 109–120, 2013.
Pico Y., Fernandez M., Ruiz M. J., dan Font G., “Current Trends in Solid-Phase-Based Extraction Techniques for the Determination of Pesticides in Food and Environment,” Journal of Biochemical and Biophysical Methods, vol. 70, pp. 117–131, 2007.
Damalas C. A. dan Koutroubas S. D., “Current Status and Recent Developments in Biopesticide Use,” Agriculture, vol. 8, p. 13, 2018.
Schlücker S., “Surface-Enhanced Raman Spectroscopy: Concepts and Chemical Applications,” Angewandte Chemie International Edition, vol. 53, pp. 4756–4795, 2014.
Le Ru E. C. dan Etchegoin P. G., “Single-Molecule Surface-Enhanced Raman Spectroscopy,” Annual Review of Physical Chemistry, vol. 63, pp. 65–87, 2012.
Moskovits M., “Surface-Enhanced Raman Spectroscopy: A Brief Retrospective,” Journal of Raman Spectroscopy, vol. 36, pp. 485–496, 2005.
Kelly K. L., Coronado E., Zhao L. L., dan Schatz G. C., “The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment,” Journal of Physical Chemistry B, vol. 107, pp. 668–677, 2003.
Nie S. dan Emory S. R., “Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering,” Science, vol. 275, pp. 1102–1106, 1997.
Stiles P. L., Dieringer J. A., Shah N. C., dan Van Duyne R. P., “Surface-Enhanced Raman Spectroscopy,” Annual Review of Analytical Chemistry, vol. 1, pp. 601–626, 2008.
Fan M., Andrade G. F. S., dan Brolo A. G., “A Review on the Fabrication of Substrates for Surface-Enhanced Raman Spectroscopy and Their Applications in Analytical Chemistry,” Analytica Chimica Acta, vol. 693, pp. 7–25, 2011.
Sharma B., Frontiera R. R., Henry A. I., et al., “SERS: Materials, Applications, and the Future,” Materials Today, vol. 15, pp. 16–25, 2012.
Hao E. dan Schatz G. C., “Electromagnetic Fields Around Silver Nanoparticles and Dimers,” Journal of Chemical Physics, vol. 120, pp. 357–366, 2004.
Camden J. P., Dieringer J. A., Wang Y., et al., “Probing the Structure of Single-Molecule SERS Hot Spots,” Journal of the American Chemical Society, vol. 130, pp. 12616–12617, 2008.
Lin X. M., Cui Y., Xu Y. H., et al., “Surface-Enhanced Raman Spectroscopy: Substrate-Related Issues,” Analytical and Bioanalytical Chemistry, vol. 394, pp. 1729–1745, 2009.
Guerrini L. dan Graham D., “Molecularly-Mediated Assemblies of Plasmonic Nanoparticles for SERS Applications,” Chemical Society Reviews, vol. 41, pp. 7085–7107, 2012.
Zhai Y., Zhai J., Wang M., et al., “Assembling and Application of Au Nanoparticle Arrays as SERS Substrate,” Applied Surface Science, vol. 257, pp. 2942–2948, 2011.
Liu B., Zhou P., Liu X., et al., “Detection of Pesticides in Fruits by Surface-Enhanced Raman Spectroscopy Coupled With Gold Nanostructures,” Food and Bioprocess Technology, vol. 6, pp. 710–718, 2013.
Dong R., Weng S., Yang L., dan Liu J., “Detection and Direct Readout of Drugs in Human Urine Using Dynamic SERS and Support Vector Machines,” Analytical Chemistry, vol. 87, pp. 2937–2944, 2015.
Craig A. P., Franca A. S., dan Irudayaraj J., “Surface-Enhanced Raman Spectroscopy Applied to Food Safety,” Annual Review of Food Science and Technology, vol. 4, pp. 369–380, 2013.
Luo H., Huang Y., Lai K., et al., “SERS-Based Detection of Melamine in Milk Powder,” Sensors and Instrumentation for Food Quality and Safety, vol. 5, pp. 91–95, 2011.
Anastassiades M., Lehotay S. J., Stajnbaher D., dan Schenck F. J., “Fast and Easy Multiresidue Method Using Acetonitrile Extraction/Partitioning and Dispersive-SPE for Determination of Pesticide Residues in Produce,” Journal of AOAC International, vol. 86, pp. 412–431, 2003.
Bell S. E. J. dan Sirimuthu N. M. S., “Quantitative Surface-Enhanced Raman Spectroscopy,” Chemical Society Reviews, vol. 37, pp. 1012–1024, 2008.
Natan M. J., “Concluding Remarks: Surface-Enhanced Raman Scattering,” Faraday Discussions, vol. 132, pp. 321–328, 2006.
Wang Y., Lee K., dan Irudayaraj J., “Silver Nanosphere SERS Probes for Sensitive Identification of Pathogens,” Journal of Physical Chemistry C, vol. 114, pp. 16122–16128, 2010.
Pilot R., Signorini R., Durante C., et al., “A Review on Surface-Enhanced Raman Scattering,” Biosensors, vol. 9, p. 57, 2019.
Egging M., Bonner T., Jeschke B. J., et al., “SERS for Food Analysis: Evaluation of Effects of Gold Nanoparticles on Nutritive Value and Toxicity,” Analytical and Bioanalytical Chemistry, vol. 407, pp. 8519–8527, 2015.
Li X., Yang T., Song Y., et al., “SERS-Based Detection for Food Safety: Recent Advances and Future Prospects,” Comprehensive Reviews in Food Science and Food Safety, vol. 20, pp. 2891–2926, 2021.
Yaseen T., Pu H., dan Sun D. W., “Functionalization Techniques for Improving SERS Substrates in Food Safety Evaluation,” Trends in Food Science and Technology, vol. 72, pp. 162–174, 2018.
Lee P. C. dan Meisel D., “Adsorption and SERS of Dyes on Silver and Gold Sols,” Journal of Physical Chemistry, vol. 86, pp. 3391–3395, 1982.
Creighton J. A., Blatchford C. G., dan Albrecht M. G., “Plasma Resonance Enhancement of Raman Scattering by Pyridine Adsorbed on Ag or Au Sols,” Journal of the Chemical Society, Faraday Transactions, vol. 75, pp. 790–798, 1979.
Lehotay S. J., Son K. A., Kwon H., et al., “Comparison of QuEChERS Sample Preparation Methods for Pesticide Residue Analysis in Fruits and Vegetables,” Journal of Chromatography A, vol. 1217, pp. 2548–2560, 2010.
ICH Expert Working Group, Validation of Analytical Procedures: Text and Methodology Q2(R1), Geneva: International Conference on Harmonisation, 2005.
Chen M., Luo W., Liu Q., et al., “Simultaneous In Situ Extraction and Fabrication of SERS Substrate for Reliable Detection of Thiram Residue,” Analytical Chemistry, vol. 90, pp. 13647–13654, 2018.
Xu Y., Kutsanedzie F. Y. H., Hassan M. M., et al., “Mesoporous Silica Supported Orderly-Spaced Gold Nanoparticles SERS-Based Sensor for Pesticide Detection in Food,” Food Chemistry, vol. 315, p. 126158, 2020.