Determination of Paraquat Using Microfluidic Paper-Based Analytical Device (µPAD) Immobilized with p-Hydroxybenzoic Acid Capped Silver Nanoparticles
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Keywords:
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Paraquat, Silver Nanoparticles, µPAD, Colorimetric Detection, Water Analysis
Abstract
This study developed a microfluidic paper-based analytical device (µPAD) immobilized with p-hydroxybenzoic acid capped silver nanoparticles (AgNPs-PHB) for the colorimetric detection of paraquat (PQ) in water samples. The synthesized AgNPs-PHB exhibited favorable properties, including a nanoscale size (68.5 nm by DLS, 20 nm by TEM), high stability (zeta potential of -53 mV), and a spherical morphology, as confirmed by UV-Vis spectroscopy, PSA, and TEM analysis. The µPAD platform utilized a wax-printed hydrophobic barrier to direct sample flow, enabling a simple and cost-effective detection method. Upon interaction with PQ, AgNPs-PHB underwent aggregation, resulting in a visible color change from yellow to gray, which was quantified using ImageJ software for RGB analysis. The method demonstrated excellent linearity (R2 = 0.9917 for red intensity) across a concentration range of 0.001 - 0.01 M, with a limit of detection (LOD) of 0.00060 M and a limit of quantification (LOQ) of 0.0020 M. Precision tests revealed high repeatability and reproducibility, with intraday and interday %RSD values below 2%. Recovery studies in tap water, drainage water, and well water samples spiked with PQ yielded accurate results (99.7–102.5%), validating the method’s reliability. Compared to conventional techniques, this µPAD-based approach offers a portable, environmentally friendly, and sensitive alternative for monitoring PQ contamination in environmental water samples, making it suitable for field applications.
References
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Çelebi, M. and E. Gökirmak Söğüt (2022). High-Efficiency Removal of Cationic Dye and HeavyMetal Ions from Aqueous Solution Using Amino-Functionalized Graphene Oxide, Adsorption Isotherms, Kinetics Studies, and Mechanism. Turkish Journal of Chemistry, 46(5); 1577–1593
Chandra, A., K. A. Shah, S. Mahato, M. S. Bhattacharjee, and T. Mandal (2021). Paraquat Poisoning. BMJ Case Reports, 14(11); e246585
Firdaus, M. L., A. Aprian, N. Meileza, M. Hitsmi, R. Elvia, L. Rahmidar, and R. Khaydarov (2019). Smartphone Coupled with a Paper-Based Colorimetric Device for Sensitive and Portable Mercury Ion Sensing. Chemosensors, 7(2); 25
Franco, D. S. P., J. Georgin, E. C. Lima, and L. F. O. Silva (2022). Advances Made in Removing Paraquat Herbicide by Adsorption Technology: A Review. Journal of Water Process Engineering, 49; 102988
Goulet, P. J. G. and R. F. Aroca (2004). Chemical Adsorption of Salicylate on Silver: A Systematic Approach to the Interpretation of Surface-Enhanced Vibrational Spectra. Canadian Journal of Chemistry, 82(6); 987–997
Gusrizal (2017). Sintesis Nanopartikel Perak Melalui Reduksi Ion Perak dengan Asam 2-, 3-, dan 4-Hidroksibenzoat serta Aplikasinya untuk Penentuan Parakuat
Gusrizal, S. J. Santosa, E. S. Kunarti, and B. Rusdiarso (2016). Dual Function of p-Hydroxybenzoic Acid as Reducing and Capping Agent in Rapid and Simple Formation of Stable Silver Nanoparticles. International Journal of ChemTech Research, 9(9); 472–482
Gusrizal, S. J. Santosa, E. S. Kunarti, and B. Rusdiarso (2018). Two Highly Stable Silver Nanoparticles: Surface Plasmon Resonance Spectra Study of Silver Nanoparticles Capped with m-Hydroxybenzoic Acid and p-Hydroxybenzoic Acid. Molekul, 13(1); 30–37
Gusrizal, S. J. Santosa, E. S. Kunarti, and B. Rusdiarso (2020). Silver Nanoparticles Capped with p-Hydroxybenzoic Acid as a Colorimetric Sensor for the Determination of Paraquat. Indonesian Journal of Chemistry, 20(3); 688–696
Heydebreck, F. (2021). Monitoring of Paraquat in Soya Products Intended for Animal Feed. International Journal of Food Contamination, 8(1); 9
Kalinke, C., A. S. Mangrich, L. H. Marcolino-Junior, and M. F. Bergamini (2016). Carbon Paste Electrode Modified with Biochar for Sensitive Electrochemical Determination of Paraquat. Electroanalysis, 28(4); 764–769
Khatoon, R., M. K. Rai, and J. K. Rai (2013). Low Cost Spectrophotometric Determination of Paraquat in Environmental and Biological Samples. Recent Research in Science and Technology, 5(2); 4–6
Kumar Majumder, K., J. B. Sharma, M. Kumar, S. Bhatt, and V. Saini (2020). A Review on Paraquat Poisoning. Pharmacophore, 11(1); 115–121
Lima, T. L., M. A. Nicoletti, C. Munhoz, G. R. de Abreu, J. Z. Magalhães, E. L. R. Ricci, P. A. F.Waziry, J. N. A. da Costa, A. C. N. Antônio, and A. R. Fukushima (2018). Determination of Paraquat in Several Commercially Available Types of Rice. Food and Nutrition Sciences, 9(12); 1368–1376
Madaniyah, L., S. Fiddaroini, E. K. Hayati, M. F. Rahman, and A. Sabarudin (2025). Stability of Biologically Synthesized Silver Nanoparticles (AgNPs) Using Acalypha indica L. Plant Extract as Bioreductor and Their Potential as Anticancer Agents Against T47D Cells. Science and Technology Indonesia, 10(1); 101–110
Moulahoum, H. (2023). Dual Chromatic Laser-Printed Microfluidic Paper-Based Analytical Device (μPAD) for the Detection of Atrazine inWater. ACS Omega, 8(44); 41194–41203
Pan, S., L.Wang, Q. Qiu, and Q. He (2022). Determination of Paraquat and Diquat Residues in Urine Samples Based on Solid-Phase Extraction and Ultra Performance Liquid Chromatography–High Resolution Mass Spectrometry. Chinese Journal of Chromatography, 40(12); 1087–1094
Paramelle, D., A. Sadovoy, S. Gorelik, P. Free, J. Hobley, and D. G. Fernig (2014). A Rapid Method to Estimate the Concentration of Citrate Capped Silver Nanoparticles from UV–Visible Light Spectra. Analyst, 139(19); 4855–4861
Pasieczna-Patkowska, S., M. Cichy, and J. Flieger (2025). Application of Fourier Transform Infrared (FTIR) Spectroscopy in Characterization of Green Synthesized Nanoparticles. Molecules, 30(3); 684
Pizzutti, I. R., G. M. E. Vela, A. de Kok, J. M. Scholten, J. V. Dias, C. D. Cardoso, G. Concenço, and R. Vivian (2016). Determination of Paraquat and Diquat: LC–MS Method Optimization and Validation. Food Chemistry, 209; 248–255
Rahman, A. K. M. F., S. Al Kafi, and Z. Naiem (2024). Study on Clinical Profile and Treatment Outcome of Acute Paraquat Poisoning in an Intensive Care Unit in Bangladesh. Journal of Medicine, 25(2); 129–135
Rohit, J. V., H. Basu, R. K. Singhal, and S. K. Kailasa (2016). Development of p-Nitroaniline Dithiocarbamate Capped Gold Nanoparticles-Based Microvolume UV–Vis Spectrometric Method for Facile and Selective Detection of Quinalphos Insecticide in Environmental Samples. Sensors and Actuators B: Chemical, 237; 826–835
Sangsum, C. and P. Saetear (2022). All-Step-in-One Test Kit for Paraquat Detection inWater and Vegetable Samples. Analytica, 3(1); 92–105
Sękowski, S., E. Olchowik-Grabarek, W. Więckowska, A. Veiko, L. Oldak, E. Gorodkiewicz, E. Karamov, N. Abdulladjanova, S. Mavlyanov, E. Lapshina, I. B. Zavodnik, and M. Zamaraeva (2020). Spectroscopic, Zeta-Potential and Surface Plasmon Resonance Analysis of Interaction between Potential Anti-HIV Tannins with Different Flexibility and Human Serum Albumin. Colloids and Surfaces B: Biointerfaces, 194; 111175
Sha, O., B. Cui, H. Liu, Y. Wang, X. Chen, L. Chen, and S.Wang (2019). A Simple and Rapid Method for Determination of Paraquat inHumanUrine and Plasma by Improved Solid Adsorption Using Equipment Built In-House. Journal of the Iranian Chemical Society, 16(10); 2071–2080
Shariati, S. and G. Khayatian (2020). Microfluidic Paper-Based Analytical Device Using Gold Nanoparticles Modified with N,N′-Bis(2-Hydroxyethyl)dithiooxamide for Detection of Hg(II) in Air, Fish and Water Samples. New Journal of Chemistry, 44(43); 18662–18667
Stuart, A. M., C. N. Merfield, F. G. Horgan, S.Willis, M. A. Watts, F. Ramírez-Muñoz, J. S. U, L. Utyasheva, M. Eddleston, M. L. Davis, L. Neumeister, M. R. Sanou, and S.Williamson (2023). Agriculture without Paraquat Is Feasible without Loss of Productivity–Lessons Learned from Phasing Out a Highly Hazardous Herbicide. Environmental Science and Pollution Research, 30(7); 16984–17008
Sununta, S., P. Rattanarat, O. Chailapakul, and N. Praphairaksit (2018). Microfluidic Paper-Based Analytical Devices for Determination of Creatinine in Urine Samples. Analytical Sciences, 34(1); 109–113
Takechi-Haraya, Y., T. Ohgita, Y. Demizu, H. Saito, K.-i. Izutsu, and K. Sakai-Kato (2022). Current Status and Challenges of Analytical Methods for Evaluation of Size and SurfaceModification of Nanoparticle-Based Drug Formulations. AAPS PharmSciTech, 23(5); 150
Takino, M., S. Daishima, and K. Yamaguchi (2000). Determination of Diquat and Paraquat in Water by Liquid Chromatography/Electrospray–Mass Spectrometry Using Volatile Ion-Pairing Reagents. Analytical Sciences, 16(7); 707–711
Wang, Y., Y.-S. Li, Z. Zhang, and D. An (2003). Surface-Enhanced Raman Scattering of Some Water-Insoluble Drugs in Silver Hydrosols. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 59(3); 589–594
Xing, X., Y. Zhou, J. Sun, D. Tang, T. Li, and K.Wu (2013). Determination of Paraquat by Cucurbit[7]uril Sensitized Fluorescence Quenching Method. Analytical Letters, 46(4); 694–705
Xiong, Y., T. Ma, H. Zhang, L. Qiu, S. Chang, Y. Yang, and F. Liang (2022). Gold Nanoparticle Functionalized Nanopipette Sensors for Electrochemical Paraquat Detection. Microchimica Acta, 189(7); 234
Yar, A., T. M. Ansari, A. Raza, and S. Manzoor (2022). Development and Validation of HPLC–UVMethod for Determination of Paraquat in Raw and Commercial Samples. Pakistan Journal of Analytical & Environmental Chemistry, 23(1); 148–155
Zhang, J., Y. Chen, Y. Xu, Z. Zhao, and X. Xu (2025). Salicylic Acid-Mediated Silver Nanoparticle Green Synthesis: Characterization, Enhanced Antimicrobial, and Antibiofilm Efficacy. Pharmaceutics, 17(4); 532
Zhao, M., Q. Wang, M. Shi, Z. Sun, H. Tang, and X. Ge (2023). Determination of Paraquat in Arabidopsis Tissues and Protoplasts by UHPLC–MS/MS. International Journal of Molecular Sciences, 24(13); e4642
Anushka, A. Bandopadhyay, and P. K.Das (2022). Paper Based Microfluidic Devices: A Review of Fabrication Techniques and Applications. The European Physical Journal Special Topics, 232(6); 781–815
Beshana, S., A. Hussen, S. Leta, and T. Kaneta (2022). Microfluidic Paper Based Analytical Devices for the Detection of Carbamate Pesticides. Bulletin of Environmental Contamination and Toxicology, 109(2); 344–351
Bhandari, S., V. S. Parihar, M. Kellomäki, and M. Mahato (2024). Highly Selective and Flexible Silver Nanoparticles-Based Paper Sensor for On-Site Colorimetric Detection of Paraquat Pesticide. RSC Advances, 14(39); 28844–28853
Çelebi, M. and E. Gökirmak Söğüt (2022). High-Efficiency Removal of Cationic Dye and HeavyMetal Ions from Aqueous Solution Using Amino-Functionalized Graphene Oxide, Adsorption Isotherms, Kinetics Studies, and Mechanism. Turkish Journal of Chemistry, 46(5); 1577–1593
Chandra, A., K. A. Shah, S. Mahato, M. S. Bhattacharjee, and T. Mandal (2021). Paraquat Poisoning. BMJ Case Reports, 14(11); e246585
Firdaus, M. L., A. Aprian, N. Meileza, M. Hitsmi, R. Elvia, L. Rahmidar, and R. Khaydarov (2019). Smartphone Coupled with a Paper-Based Colorimetric Device for Sensitive and Portable Mercury Ion Sensing. Chemosensors, 7(2); 25
Franco, D. S. P., J. Georgin, E. C. Lima, and L. F. O. Silva (2022). Advances Made in Removing Paraquat Herbicide by Adsorption Technology: A Review. Journal of Water Process Engineering, 49; 102988
Goulet, P. J. G. and R. F. Aroca (2004). Chemical Adsorption of Salicylate on Silver: A Systematic Approach to the Interpretation of Surface-Enhanced Vibrational Spectra. Canadian Journal of Chemistry, 82(6); 987–997
Gusrizal (2017). Sintesis Nanopartikel Perak Melalui Reduksi Ion Perak dengan Asam 2-, 3-, dan 4-Hidroksibenzoat serta Aplikasinya untuk Penentuan Parakuat
Gusrizal, S. J. Santosa, E. S. Kunarti, and B. Rusdiarso (2016). Dual Function of p-Hydroxybenzoic Acid as Reducing and Capping Agent in Rapid and Simple Formation of Stable Silver Nanoparticles. International Journal of ChemTech Research, 9(9); 472–482
Gusrizal, S. J. Santosa, E. S. Kunarti, and B. Rusdiarso (2018). Two Highly Stable Silver Nanoparticles: Surface Plasmon Resonance Spectra Study of Silver Nanoparticles Capped with m-Hydroxybenzoic Acid and p-Hydroxybenzoic Acid. Molekul, 13(1); 30–37
Gusrizal, S. J. Santosa, E. S. Kunarti, and B. Rusdiarso (2020). Silver Nanoparticles Capped with p-Hydroxybenzoic Acid as a Colorimetric Sensor for the Determination of Paraquat. Indonesian Journal of Chemistry, 20(3); 688–696
Heydebreck, F. (2021). Monitoring of Paraquat in Soya Products Intended for Animal Feed. International Journal of Food Contamination, 8(1); 9
Kalinke, C., A. S. Mangrich, L. H. Marcolino-Junior, and M. F. Bergamini (2016). Carbon Paste Electrode Modified with Biochar for Sensitive Electrochemical Determination of Paraquat. Electroanalysis, 28(4); 764–769
Khatoon, R., M. K. Rai, and J. K. Rai (2013). Low Cost Spectrophotometric Determination of Paraquat in Environmental and Biological Samples. Recent Research in Science and Technology, 5(2); 4–6
Kumar Majumder, K., J. B. Sharma, M. Kumar, S. Bhatt, and V. Saini (2020). A Review on Paraquat Poisoning. Pharmacophore, 11(1); 115–121
Lima, T. L., M. A. Nicoletti, C. Munhoz, G. R. de Abreu, J. Z. Magalhães, E. L. R. Ricci, P. A. F.Waziry, J. N. A. da Costa, A. C. N. Antônio, and A. R. Fukushima (2018). Determination of Paraquat in Several Commercially Available Types of Rice. Food and Nutrition Sciences, 9(12); 1368–1376
Madaniyah, L., S. Fiddaroini, E. K. Hayati, M. F. Rahman, and A. Sabarudin (2025). Stability of Biologically Synthesized Silver Nanoparticles (AgNPs) Using Acalypha indica L. Plant Extract as Bioreductor and Their Potential as Anticancer Agents Against T47D Cells. Science and Technology Indonesia, 10(1); 101–110
Moulahoum, H. (2023). Dual Chromatic Laser-Printed Microfluidic Paper-Based Analytical Device (μPAD) for the Detection of Atrazine inWater. ACS Omega, 8(44); 41194–41203
Pan, S., L.Wang, Q. Qiu, and Q. He (2022). Determination of Paraquat and Diquat Residues in Urine Samples Based on Solid-Phase Extraction and Ultra Performance Liquid Chromatography–High Resolution Mass Spectrometry. Chinese Journal of Chromatography, 40(12); 1087–1094
Paramelle, D., A. Sadovoy, S. Gorelik, P. Free, J. Hobley, and D. G. Fernig (2014). A Rapid Method to Estimate the Concentration of Citrate Capped Silver Nanoparticles from UV–Visible Light Spectra. Analyst, 139(19); 4855–4861
Pasieczna-Patkowska, S., M. Cichy, and J. Flieger (2025). Application of Fourier Transform Infrared (FTIR) Spectroscopy in Characterization of Green Synthesized Nanoparticles. Molecules, 30(3); 684
Pizzutti, I. R., G. M. E. Vela, A. de Kok, J. M. Scholten, J. V. Dias, C. D. Cardoso, G. Concenço, and R. Vivian (2016). Determination of Paraquat and Diquat: LC–MS Method Optimization and Validation. Food Chemistry, 209; 248–255
Rahman, A. K. M. F., S. Al Kafi, and Z. Naiem (2024). Study on Clinical Profile and Treatment Outcome of Acute Paraquat Poisoning in an Intensive Care Unit in Bangladesh. Journal of Medicine, 25(2); 129–135
Rohit, J. V., H. Basu, R. K. Singhal, and S. K. Kailasa (2016). Development of p-Nitroaniline Dithiocarbamate Capped Gold Nanoparticles-Based Microvolume UV–Vis Spectrometric Method for Facile and Selective Detection of Quinalphos Insecticide in Environmental Samples. Sensors and Actuators B: Chemical, 237; 826–835
Sangsum, C. and P. Saetear (2022). All-Step-in-One Test Kit for Paraquat Detection inWater and Vegetable Samples. Analytica, 3(1); 92–105
Sękowski, S., E. Olchowik-Grabarek, W. Więckowska, A. Veiko, L. Oldak, E. Gorodkiewicz, E. Karamov, N. Abdulladjanova, S. Mavlyanov, E. Lapshina, I. B. Zavodnik, and M. Zamaraeva (2020). Spectroscopic, Zeta-Potential and Surface Plasmon Resonance Analysis of Interaction between Potential Anti-HIV Tannins with Different Flexibility and Human Serum Albumin. Colloids and Surfaces B: Biointerfaces, 194; 111175
Sha, O., B. Cui, H. Liu, Y. Wang, X. Chen, L. Chen, and S.Wang (2019). A Simple and Rapid Method for Determination of Paraquat inHumanUrine and Plasma by Improved Solid Adsorption Using Equipment Built In-House. Journal of the Iranian Chemical Society, 16(10); 2071–2080
Shariati, S. and G. Khayatian (2020). Microfluidic Paper-Based Analytical Device Using Gold Nanoparticles Modified with N,N′-Bis(2-Hydroxyethyl)dithiooxamide for Detection of Hg(II) in Air, Fish and Water Samples. New Journal of Chemistry, 44(43); 18662–18667
Stuart, A. M., C. N. Merfield, F. G. Horgan, S.Willis, M. A. Watts, F. Ramírez-Muñoz, J. S. U, L. Utyasheva, M. Eddleston, M. L. Davis, L. Neumeister, M. R. Sanou, and S.Williamson (2023). Agriculture without Paraquat Is Feasible without Loss of Productivity–Lessons Learned from Phasing Out a Highly Hazardous Herbicide. Environmental Science and Pollution Research, 30(7); 16984–17008
Sununta, S., P. Rattanarat, O. Chailapakul, and N. Praphairaksit (2018). Microfluidic Paper-Based Analytical Devices for Determination of Creatinine in Urine Samples. Analytical Sciences, 34(1); 109–113
Takechi-Haraya, Y., T. Ohgita, Y. Demizu, H. Saito, K.-i. Izutsu, and K. Sakai-Kato (2022). Current Status and Challenges of Analytical Methods for Evaluation of Size and SurfaceModification of Nanoparticle-Based Drug Formulations. AAPS PharmSciTech, 23(5); 150
Takino, M., S. Daishima, and K. Yamaguchi (2000). Determination of Diquat and Paraquat in Water by Liquid Chromatography/Electrospray–Mass Spectrometry Using Volatile Ion-Pairing Reagents. Analytical Sciences, 16(7); 707–711
Wang, Y., Y.-S. Li, Z. Zhang, and D. An (2003). Surface-Enhanced Raman Scattering of Some Water-Insoluble Drugs in Silver Hydrosols. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 59(3); 589–594
Xing, X., Y. Zhou, J. Sun, D. Tang, T. Li, and K.Wu (2013). Determination of Paraquat by Cucurbit[7]uril Sensitized Fluorescence Quenching Method. Analytical Letters, 46(4); 694–705
Xiong, Y., T. Ma, H. Zhang, L. Qiu, S. Chang, Y. Yang, and F. Liang (2022). Gold Nanoparticle Functionalized Nanopipette Sensors for Electrochemical Paraquat Detection. Microchimica Acta, 189(7); 234
Yar, A., T. M. Ansari, A. Raza, and S. Manzoor (2022). Development and Validation of HPLC–UVMethod for Determination of Paraquat in Raw and Commercial Samples. Pakistan Journal of Analytical & Environmental Chemistry, 23(1); 148–155
Zhang, J., Y. Chen, Y. Xu, Z. Zhao, and X. Xu (2025). Salicylic Acid-Mediated Silver Nanoparticle Green Synthesis: Characterization, Enhanced Antimicrobial, and Antibiofilm Efficacy. Pharmaceutics, 17(4); 532
Zhao, M., Q. Wang, M. Shi, Z. Sun, H. Tang, and X. Ge (2023). Determination of Paraquat in Arabidopsis Tissues and Protoplasts by UHPLC–MS/MS. International Journal of Molecular Sciences, 24(13); e4642
Authors
Gusrizal, G., Budi, F. S., & Puspita, D. . (2026). Determination of Paraquat Using Microfluidic Paper-Based Analytical Device (µPAD) Immobilized with p-Hydroxybenzoic Acid Capped Silver Nanoparticles . Science and Technology Indonesia, 11(1), 323–334. https://doi.org/10.26554/sti.2026.11.1.323-334
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