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Development of Copper Nanoclusters-Based Turn-Off Nanosensor for Fluorescence Detection of Two Pyrethroid Pesticides (Cypermethrin and Lambda-Cyhalothrin)

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Abstract

Fluorescent copper nanoclusters (Cu NCs) were synthesized by using Withania somnifera (W. somnifera) plant extract as a biotemplate. Aqueous dispersion of W. somnifera-Cu NCs displays intense emission peak at 458 nm upon excitation at 350 nm. This fluorescence emission was utilized for the detection of two pyrethroid pesticides (cypermethrin and lambda-cyhalothrin) via “turn-off” mechanism. Upon the addition of two pyrethiod pesticides independently, the fluorescence emission of W. somnifera-Cu NCs was gradually decreased with increasing concentrations of both pesticides. It was noticed that the decrease in emission intensity at 458 nm was linearly dependent on the logarithm of both pesticides concentrations in the ranges of 0.01–100 μM and of 0.05–100 μM for cypermethrin and lambda-cyhalothrin, respectively. Consequently, the limits of detection were found to be 27.06 and 23.28 nM for cypermethrin and lambda-cyhalothrin, respectively. The as-fabricated W. somnifera-Cu NCs acted as a facile sensor for the analyses of cypermethrin and lambda-cyhalothrin in vegetables (tomato and bottle gourd), which demonstrates that it could be used as portable sensing platform for assaying of two pyrethroid pesticides in food samples.

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5. References

  1. Yadav IC, Devi NL (2017) Pesticides classification and its impact on human and environment. Environ Sci Engg 6:140–158

    Google Scholar 

  2. Weis G, Alves A, Assmann C, Bonadiman B, Hilda I (2019) Pesticides: classifications, exposure and risks to human health. Arch Biol Sci 1:29–44

    Google Scholar 

  3. Kansal I, Kapoor A, Solanki S, Singh R (2023) Cypermethrin toxicity in the environment: analytical insight into detection methods and microbial degradation pathways. J Appl Microbiol 134(6):lxad105

  4. Pérez JJ, Williams MK, Weerasekera G, Smith K, Whyatt RM, Needham LL, Barr DB (2010) Measurement of Pyrethroid, Organophosphorus, and Carbamate Insecticides in Human Plasma using Isotope Dilution Gas Chromatography-High Resolution Mass Spectrometry. J Chromatogr B Anal Technol Biomed Life Sci 878:2554–2562

  5. Janghel EK, Rai JK, Rai MK, Gupta VK (2007) A new sensitive spectrophotometric determination of cypermethrin insecticide in environmental and biological samples. J Braz Chem Soc 18:590–594

    Article  CAS  Google Scholar 

  6. Bengston M, Davies R, Desmarchelier JM, Henning R, Murray W, Simpson B, Snelson JT, Sticka R, Wallbank B (2014) Organophosphorothioates and synergised synthetic pyrethroids as grain protectants on bulk wheat. Pestic Sci 4:373–384

    Google Scholar 

  7. Puente C, Pineda N, López I (2023) Cypermethrin insecticide detection by surface-enhanced Raman spectroscopy. J Chem Technol Biotechnol 98:1863–1867

    Article  CAS  Google Scholar 

  8. Anadon A, Martinez M, Martinez MA, Diaz MJ, Martinez MR (2006) Larranaga, Toxicokinetics of λ-cyhalothrin in rats. Toxicol Lett 1:47–56

    Article  Google Scholar 

  9. Lofty HM, Abd El AE, Monir HH (2013) Determination of insecticides malathion and λ-cyhalothrin residues in zucchini by gas chromatography. Bull Fac Pharm Cairo Univ 2:255–260

  10. Liu S, Yao K, Jia D, Zhao N, Lai W, Yuan H (2012) A Pretreatment Method for HPLC Analysis of Cypermethrin in Microbial Degradation Systems. J Chromatogr Sci 50:469–476

    Article  PubMed  CAS  Google Scholar 

  11. Li J, Lin D, Ji R, Yao K, Deng WQ, Yuan H, Wu Q, Jia Q, Luo P, Zhou K, He L (2016) Simultaneous Determination of β-Cypermethrin and Its Metabolite 3-Phenoxybenzoic Acid in Microbial Degradation Systems by HPLC–UV. J Chromatographic Sci 54:1584–1592

  12. Personne S, Marcelo P, Pilard S, Baltora-Rosset S, Corona A, Robidel F, Lecomte A, Brochot C, Bach V, Zeman F (2019) Determination of maternal and foetal distribution of cis- and trans-permethrin isomers and their metabolites in pregnant rats by liquid chromatography tandem mass spectrometry (LC-MS/MS). Anal Bioanal Chem 411:8043–8052

    Article  PubMed  CAS  Google Scholar 

  13. Nurdin M, Maulidiyah M, Muzakkar MZ, Umar AA (2019) High performance cypermethrin pesticide detection using anatase TiO2-carbon paste nanocomposites electrode. Microchemical J 145:756–761

  14. Lofty HM, Abd El AE, Monir HH (2013) Determination of insecticides malathion and lambda-cyhalothrin residues in zucchini by gas chromatography. Bull Fac Pharm Cairo Univ 51:255–260

  15. Khatoon R, Uddin R, Khurshid S, Anwar F, Iqbal S, Baloch PA, Khan A (2022) Determination of Lambda-Cyhalothrin and Malathion Residues in Locust by Gas Chromatography with Electron Capture Detection. J Anal Chem 77:611–617

    Article  Google Scholar 

  16. Zheng J, Gong Z, Yin S, Wang W, Wang M, Lin P, Zhou H, Yang Y (2022) Rapid determination of lambda-cyhalothrin residues on Chinese cabbage based on MIR spectroscopy and a Gustafson–Kessel noise clustering algorithm. RSC Adv 12:18457–18465

  17. Wang X, Zhao X, Liu X, Li Y, Fu L, Hu J, Huang C (2008) Homogeneous liquid–liquid extraction combined with gas chromatography–electron capture detector for the determination of three pesticide residues in soils. Anal Chim 1–2:162–169

    Article  Google Scholar 

  18. Djouaka R, Soglo MF, Kusimo MO, Adéoti R, Talom A, Zeukeng F, Paraïso A, Afari-Sefa V, Saethre MG, Manyong V, Tamò M (2018) The rapid degradation of lambda-cyhalothrin makes treated vegetables relatively safe for consumption. Int J Environ Res Public Health 15(7):1536

    Article  PubMed  PubMed Central  Google Scholar 

  19. Huang X, Zhao X, Lu X, Tian H, Xu A, Liu Y, Jian Z (2014) Simultaneous determination of 50 residual pesticides in Flos Chrysanthemi using accelerated solvent extraction and gas chromatography. J Chromatogr B 967:1–7

    Article  CAS  Google Scholar 

  20. Zhao D, Liu X, Shi W, Liu R (2011) Determination of cypermethrin residues in crucian carp tissues by MSPD/GC-ECD. Chromatographia 73:1021–1025

    Article  CAS  Google Scholar 

  21. Deme P, Azmeera T, Prabhavathi BLA, Jonnalagadda PR, Prasad RBN, Sarathi UVR (2014) An improved dispersive solid-phase extraction clean-up method for the gas chromatography–negative chemical ionisation tandem mass spectrometric determination of multiclass pesticide residues in edible oils. Food Chem 142:144–151

    Article  PubMed  CAS  Google Scholar 

  22. Esteve T, Francesc A, Pastor A, Guardia M (2006) Comparison of different mass spectrometric detection techniques in the gas chromatographic analysis of pyrethroid insecticide residues in soil after microwave-assisted extraction. Anal Bioanal Chem 384:801–809

    Article  Google Scholar 

  23. Sami B, Paisse O, Loustalot G (2003) Determination of residual pesticides in olive oil by GC-MS and HPLC-MS after extraction by size-exclusion chromatography. Anal Bioanal Chem 376:355–359

    Article  Google Scholar 

  24. Wang Y, Wang M, Sun X, Shi G, Zhang J, Ma W, Ren L (2018) Grating-like SERS substrate with tunable gaps based on nanorough Ag nanoislands/moth wing scale arrays for quantitative detection of cypermethrin. Opt Express 17:22168–22181

    Article  Google Scholar 

  25. Zhang R, Li X, Sun A, Song S, Shi X (2022) A highly selective fluorescence nanosensor based on the dual-function molecularly imprinted layer coated quantum dots for the sensitive detection of diethylstilboestrol/cypermethrin in fish and seawater. Food Control 132:108438

    Article  CAS  Google Scholar 

  26. Wang J, Gao L, Han D, Pan J, Qiu H, Li H (2015) Optical detection of λ-cyhalothrin by core–shell fluorescent molecularly imprinted polymers in Chinese spirits. J Agric Food Chem 9:2392–2399

    Article  Google Scholar 

  27. Zhang D, Tang J, Liu H (2019) Rapid determination of lambda-cyhalothrin using a fluorescent probe based on ionic-liquid-sensitized carbon dots coated with molecularly imprinted polymers. Anal Bioanal Chem 411:5309–5316

    Article  PubMed  CAS  Google Scholar 

  28. Kailasa SK, Borse S, Koduru JR, Murthy ZVP (2021) Biomolecules as promising ligands in the synthesis of metal nanoclusters: Sensing, bioimaging and catalytic applications. Trends Environ Anal Chem 32:e00140

    Article  CAS  Google Scholar 

  29. Harshita TJ, Park SK (2023) Kailasa, Microwave-assisted synthesis of blue fluorescent molybdenum nanoclusters with maltose-cysteine Schiff base for detection of myoglobin and γ-aminobutyric acid in biofluids. Luminescence 38:1374–1384

    Article  PubMed  CAS  Google Scholar 

  30. Qing T, Zhang K, Qing Z, Wang X, Long C, Zhang P, Hu H, Feng B (2019) Recent progress in copper nanocluster-based fluorescent probing: a review. Mikrochim Acta 186:1–20

    Article  CAS  Google Scholar 

  31. Liu X, Astruc D (2018) Atomically precise copper nanoclusters and their applications. Coord Chem Rev 359:112–126

    Article  CAS  Google Scholar 

  32. Borse S, Murthy ZVP, Kailasa SK (2023) Fabrication of water-soluble blue emitting molybdenum nanoclusters for sensitive detection of cancer drug methotrexate. J Photochem Photobiol A 435:114323

    Article  CAS  Google Scholar 

  33. Borse S, Murthy ZVP, Kailasa SK (2022) Synthesis of red emissive copper nanoclusters with 2-mercaptopyrimidine for promoting selective and sensitive fluorescent sensing of creatinine as a kidney disease biomarker in biofluids. J Mol Liq 368:120705

    Article  CAS  Google Scholar 

  34. Guo Y, Cao F, Lei X, Mang L, Cheng S, Song J (2016) Fluorescent copper nanoparticles: recent advances in synthesis and applications for sensing metal ions. Nanoscale 9:4852–4863

    Article  Google Scholar 

  35. Atulbhai SV, Singhal RK, Basu H, Kailasa SK (2023) Perspectives of different colour-emissive nanomaterials in fluorescent ink, LEDs, cell imaging, and sensing of various analytes. Luminescence 38:867–895

    Article  PubMed  CAS  Google Scholar 

  36. Ren Y, Bick M, Dudek A, Waworuntu E, Tang J, Chen J, Chang B (2020) Highly fluorescent copper nanoclusters for sensing and bioimaging. Biosens Bioelectron 154:112078

    Article  PubMed  Google Scholar 

  37. Harshita TJ, Park SK (2023) Kailasa, Microwave assisted synthesis of green fluorescent copper nanoclusters: A novel approach for sensing of hydroxyl radical and pyrophosphate ion via “turn-off-on” mechanism. New J Chem. https://doi.org/10.1039/D3NJ03751G

    Article  Google Scholar 

  38. Hu X, Mao X, Zhang X, Huang Y (2017) One-step synthesis of orange fluorescent copper nanoclusters for sensitive and selective sensing of Al3+ ions in food samples. Sens Actuators B Chem 247:312–318

    Article  CAS  Google Scholar 

  39. Lam NH, Smith RP, Le N, Thuy CTT, Tamboli MS, Tamboli AM, Alshehri S, Ghoneim MM, Truong NTN, Jung JH (2022) Evaluation of the Structural Deviation of Cu/Cu2O Nanocomposite Using the X-ray Diffraction Analysis Methods. Crystals 12(4):566

    Article  CAS  Google Scholar 

  40. Li Y, Zhang L, Dang Y, Chen Z, Zhang R, Li Y, Ye B (2019) A robust electrochemical sensing of molecularly imprinted polymer prepared by using bifunctional monomer and its application in detection of cypermethrin. Biosens Bioelectron 127:207–214

    Article  PubMed  CAS  Google Scholar 

  41. Zhao Y, Ruan X, Song Y, Smith J, Vasylieva N, Hammock B, Lin Y, Du D (2021) Smartphone-based dual-channel immunochromatographic test strip with polymer quantum dot labels for simultaneous detection of cypermethrin and 3-phenoxybenzoic acid. Anal Chem 40:13658–13666

    Article  Google Scholar 

  42. Lee HJ, Shan G, Ahn KC, Park EK, Watanabe T, Gee SJ, Hammock BD (2004) Development of an enzyme-linked immunosorbent assay for the pyrethroid cypermethrin. J Agric Food Chem 52:1039–1043

    Article  PubMed  CAS  Google Scholar 

  43. Leung W, Limwichean S, Nuntawong N, Eiamchai P, Kalasung S, Nimittrakoolchai O, Houngkamhang N (2020) Rapid detection of cypermethrin by using surface-enhanced Raman scattering technique. Key Eng Mater 853:102–106

    Article  Google Scholar 

  44. Muhammad M, Khan S, Rahim G, Alharbi W, Alharbi KH (2022) Highly selective and sensitive spectrofluorimetric method for determination of cypermethrin in different in different environmental samples. Environ Monit Assess 12:890

    Article  Google Scholar 

  45. Bhamore J, Jha S, Basu H, Singhal RK, Murthy ZVP, Kailasa SK (2018) Tuning of gold nanoclusters sensing applications with bovine serum albumin and bromelain for detection of Hg2+ ion and lambda-cyhalothrin via fluorescence turn-off and on mechanisms. Anal Bioanal Chem 410:2781–2791

    Article  PubMed  CAS  Google Scholar 

  46. Wang X, Zhao X, Liu X, Li Y, Fu L, Hu J, Huang C (2008) Homogeneous liquid–liquid extraction combined with gas chromatography electron capture detector for the determination of three pesticide residues in soils. Anal Chim Acta 1–2:162–169

    Article  Google Scholar 

  47. Oudou HC, Alonso RM, Hansen HC (2004) Voltammetric behaviour of the synthetic pyrethroid λ-cyhalothrin and its determination in soil and well water. Anal Chim Acta 1:69–74

    Article  Google Scholar 

  48. Nana L, Ruiyi L, Wang G, Haiyan Z, Li Z (2022) A nickel oxide nickel Chinese quantum dot self-healing hydrogel for colorimetric detection and removal of λ-cyhalothrin in kumquat. New J Chem 19:9408–9417

    Article  Google Scholar 

  49. Zhang D, Tang J, Liu H (2019) Rapid determination of λ-cyhalothrin using a fluorescent probe based on ionic-liquid-sensitized carbon dots coated with molecularly imprinted polymers. Anal Bioanal Chem 411:5309–5316

    Article  PubMed  CAS  Google Scholar 

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Acknowledgements

SN thanks the Director, SVNIT, Surat for providing infrastructural facilities to perform this work.

Funding

This work was financially supported by the Gujarat State Biotechnology Mission (GSBTM), DST, Govt. of Gujarat, India (BR-04 (GSBTM/JD(R&D)662/2022-23/00292169).

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Authors and Affiliations

  1. Department of Chemistry, Sardar Vallabhbhai National Institute of Technology, Surat, 395 007, India

    Satyaprakash Nayak, Shraddha Borse & Suresh Kumar Kailasa

  2. ASPEE SHAKILAM Biotechnology Institute, Navsari Agricultural University, Surat, 395007, Gujarat, India

    Sanjay Jha & Vaibhavkumar N. Mehta

  3. Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology, Surat, 395 007, India

    Z. V. P. Murthy

  4. Department of Chemistry, Research Institute of Chem-Bio Diagnostic Technology, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul, 06974, Republic of Korea

    Tae Jung Park

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  1. Satyaprakash Nayak
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Contributions

Satyaprakash Nayak: Methodology, Formal analysis, Writing—Review and Editing. Shraddha Borse: Formal analysis, Writing—Review and Editing. Sanjay Jha: Material preparation, Formal analysis, Writing—Review and Editing. Vaibhavkumar N.Mehta: Methodology, Formal analysis. Z. V. P. Murthy: Formal analysis, Writing—Review and Editing. Tae Jung Park: Writing—Review and Editing. Suresh Kumar Kailasa: Conception and design, Data collection and analysis, Formal analysis and Investigation, Software, Writing review, Editing and Funding.

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Correspondence to Suresh Kumar Kailasa.

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Nayak, S., Borse, S., Jha, S. et al. Development of Copper Nanoclusters-Based Turn-Off Nanosensor for Fluorescence Detection of Two Pyrethroid Pesticides (Cypermethrin and Lambda-Cyhalothrin). J Fluoresc (2023). https://doi.org/10.1007/s10895-023-03537-0

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