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Fluorometric determination of acetamiprid using molecularly imprinted upconversion nanoparticles

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Abstract

This paper describes the fabrication of an imprinted fluorescent nanoprobe based on SiO2-coated NaYF4: Yb, Er upconversion nanoparticles (UCNP) encapsulated with a molecularly imprinted polymer (MIP) for determination of acetamiprid. The fluorescent MIP nanoprobe was prepared using UCNP as the material for fluorescence signal readout, acetamiprid as template molecule, methylacrylic acid (MAA) as functional monomer, and ethyleneglycol dimethacrylate (EGDMA) as cross-linking agent. The molecular imprinting layers were immobilized on the surface of the UCNP@SiO2 by polymerization which occurred between the double bonds. UCNP@MIP shows a high selectivity towards acetamiprid with an imprinting factor (IF) of 7.84. When UCNP@MIP combines with acetamiprid, the fluorescence of the UCNP@MIP can be quenched due to the photo-induced electron transfer. Under optimum conditions, the fluorescence method shows a good linear relationship between the decreased fluorescence intensity (with excitation/emission peaks at 980/542 nm) and the variation of acetamiprid in the concentration range 20 to 800 ng mL−1. The limit of detection (LOD) is 8.3 ng mL−1. This fluorescence method was also successfully applied to detect acetamiprid in apple and strawberry samples. The recoveries range from 89.6 to 97.9%, with relative standard deviations between 1.6 and 2.9% (n = 5).

A simple fluorescence nanoprobe which integrates upconversion nanoparticles (UCNPs) and molecular imprinting polymer (MIP) was developed for the determination of acetamiprid. The limit of the detection was determined as 8.3 ng mL−1. The selectivity was enhanced by molecular imprinting, and the sensitivity was improved by the high sensitivity of the fluorescence emitted from the UCNPs.

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References

  1. Abdollahzadeh G, Sharifzadeh MS, Damalas CA (2015) Perceptions of the beneficial and harmful effects of pesticides among Iranian rice farmers influence the adoption of biological control. Crop Prot 75:124–131

    Article  Google Scholar 

  2. Jeschke P, Nauen R (2010) Neonicotinoids-from zero to hero in insecticide chemistry. Pest Manag Sci 64:1084–1098

    Article  Google Scholar 

  3. Li R, Li SC, Liu J (2011) Studies of hemocytes DNA damage by two pesticides acetamiprid and chlorpyrifos in predaceous spiders of Pardosa astrigera Koch. Acta Ecol Sin 31:3156–3162

    CAS  Google Scholar 

  4. Yeter O, Aydin A (2014) Determination of acetamiprid and IM-1-2 in postmortem human blood, liver, stomach contents by HPLC-DAD. J Forensic Sci 59:287–292

    Article  CAS  Google Scholar 

  5. Mateusánchez M, Moreno M, Arrebola FJ, Martínez Vidal JL (2003) Analysis of acetamiprid in vegetables using gas chromatography-tandem mass spectrometry. Anal Sci 19:701–704

    Article  Google Scholar 

  6. Watanabe E, Miyake S, Baba K, Eun H, Endo S (2006) Immunoassay for acetamiprid detection: application to residue analysis and comparison with liquid chromatography. Anal Bioanal Chem 386:1441–1448

    Article  CAS  Google Scholar 

  7. Watanabe E, Yamasaki T, Hirakawa Y, Harada A, Iwasa S, Miyake S (2018) Organic solvent-free immunoassay for quantitative detection of neonicotinoid acetamiprid residues in agricultural products. Anal Methods-UK 10:3162–3169

    Article  CAS  Google Scholar 

  8. He J, Liu Y, Fan M, Liu X (2011) Isolation and identification of the DNA aptamer target to acetamiprid. J Agric Food Chem 59:1582–1586

    Article  CAS  Google Scholar 

  9. Guo J, Li Y, Wang L, Xu J, Huang Y, Luo Y, Shen F, Sun C, Meng R (2015) Aptamer-based fluorescent screening assay for acetamiprid via inner filter effect of gold nanoparticles on the fluorescence of CdTe quantum dots. Anal Bioanal Chem 408:557–566

    Article  Google Scholar 

  10. Yang L, Sun H, Wang X (2019) An aptamer based aggregation assay for the neonicotinoid insecticide acetamiprid using fluorescent upconversion nanoparticles and DNA functionalized gold nanoparticles. Microchim Acta 17:323–328

    Google Scholar 

  11. Guo Y, Xiao L, Wang Y, Liu Y, Zhu G, Gui W (2013) Cyclodextrin-based molecularly imprinted polymers for the efficient recognition of pyrethroids in aqueous media. J Appl Polym Sci 128:4014–4022

    Article  CAS  Google Scholar 

  12. Tang K, Gu X, Luo Q, Chen S, Wu L, Xiong J (2014) Preparation of molecularly imprinted polymer for use as SPE adsorbent for the simultaneous determination of five sulphonylurea herbicides by HPLC. Food Chem 150:106–112

    Article  CAS  Google Scholar 

  13. Davoodi D, Hassanzadeh-Khayyat M, Rezaei MA, Mohajeri SA (2014) Preparation, evaluation and application of diazinon imprinted polymers as the sorbent in molecularly imprinted solid-phase extraction and liquid chromatography analysis in cucumber and aqueous samples. Food Chem 158:421–428

    Article  CAS  Google Scholar 

  14. Feng F, Zheng J, Qin P, Han T, Zhao D (2017) A novel quartz crystal microbalance sensor array based on molecular imprinted polymers for simultaneous detection of clenbuterol and its metabolites. Talanta 167:94–102

    Article  CAS  Google Scholar 

  15. Gao D, Wang DD, Fu QF, Wang LJ, Zhang LK, Yang FQ, Xia ZN (2018) Preparation and evaluation of magnetic molecularly imprinted polymers for the specific enrichment of phloridzin. Talanta 178:299–307

    Article  CAS  Google Scholar 

  16. Bagheri H, Molaei K, Asgharinezhad AA, Ebrahimzadeh H, Shamsipur M (2016) Magnetic molecularly imprinted composite for the selective solid-phase extraction of p-aminosalicylic acid followed by high-performance liquid chromatography with ultraviolet detection. J Sep Sci 39:4166–4174

    Article  CAS  Google Scholar 

  17. Wang YY, Wang JX, Cheng RJ, Sun L, Dai XH, Yan YS (2018) Synthesis of molecularly imprinted dye-silica nanocomposites with high selectivity and sensitivity: fluorescent imprinted sensor for rapid and efficient detection of τ-fluvalinate in vodka. J Sep Sci 41:1880–1887

  18. Li H, Xiao W, Xu Y, Kai L, Zhang Y, Yan Y, Li C (2017) A thin shell and “sunny shape” molecular imprinted fluorescence sensor in selective detection of trace level pesticides in river. J Alloys Compd 705:524–532

    Article  CAS  Google Scholar 

  19. Wu SJ, Nuo D, Ma XY, Yu X, Wang HX, Wang ZP, Zhang Q (2012) Multiplexed fluorescence resonance energy transfer aptasensor between upconversion nanoparticles and graphene oxide for the simultaneous determination of mycotoxins. Anal Chem 84:6263–6270

    Article  CAS  Google Scholar 

  20. Wu SJ, Zhang H, Shi Z, Duan N, Fang CC, Dai SL, Wang ZP (2015) Aptamer-based fluorescence biosensor for chloramphenicol determination using upconversion nanoparticles. Food Control 50:597–604

    Article  CAS  Google Scholar 

  21. Tang YW, Gao ZY, Wang S, Gao X, Gao JW, Ma Y, Liu XY, Li JR (2015) Upconversion particles coated with molecularly imprinted polymers as fluorescence probe for detection of clenbuterol. Biosens Bioelectron 71:7144–7150

    Google Scholar 

  22. Tang YW, Li M, Gao ZY, Liu XY, Gao X, Ma T, Lu XN, Li JR (2017) Upconversion nanoparticles capped with molecularly imprinted polymer as fluorescence probe for the determination of ractopamine in water and pork. Food Anal Methods 10:2964–2973

    Article  Google Scholar 

  23. Qian K, Fang G, Wang S (2013) Highly sensitive and selective novel core–shell molecularly imprinted polymer based on NaYF4: Yb3+, Er3+ upconversion fluorescent nanorods. RSC Adv 3:3825–3828

    Article  CAS  Google Scholar 

  24. Dai SL, Wu SJ, Duan N, Chen J, Zheng ZG, Wang ZP (2017) An ultrasensitive aptasensor for Ochratoxin A using hexagonal core/shell upconversion nanoparticles as luminophores. Biosens Bioelectron 91:538–544

  25. Wu SJ, Duan N, Wang ZP, Wang HX (2011) Aptamer-functionalized magnetic nanoparticle-based bioassay for the detection of ochratoxin A using upconversion nanoparticles as labels. Analyst 136:2306–2314

    Article  CAS  Google Scholar 

  26. Jin Y, Row KH (2005) Adsorption isotherm of ibuprofen on molecular imprinted polymer. Korean J Chem Eng 22:264–267

    Article  CAS  Google Scholar 

  27. Umpleby RJ, Baxter SC, Chen Y, Shah RN, Shimizu KD (2001) Characterization of molecularly imprinted polymers with the Langmuir-Freundlich isotherm. Anal Chem 73:4584–4591

    Article  CAS  Google Scholar 

  28. Bauer A, Westkamper F, Grimme S, Bach T (2005) Catalytic enantioselective reactions driven by photoinduced electron transfer. Nature 436:1139–1140

    Article  CAS  Google Scholar 

  29. Doose S, Neuweiler H, Sauer M (2010) Fluorescence quenching by photoinduced electron transfer: a reporter for conformational dynamics of macromolecules. Chemphyschem 10:1389–1398

    Article  Google Scholar 

  30. Zhao GJ, Liu JY, Zhou LC, Han KL (2007) Site-selective photoinduced electron transfer from alcoholic solvents to the chromophore facilitated by hydrogen bonding: a new fluorescence quenching mechanism. J Phys Chem B 111:8940–8945

    Article  CAS  Google Scholar 

  31. Tang YW, Li M, Gao X, Liu XY, Gao JW, Ma T, Li JR (2017) A NIR-responsive up-conversion nanoparticle probe of the NaYF4:Er,Yb type and coated with a molecularly imprinted polymer for fluorometric determination of enrofloxacin. Microchim Acta 184:3469–3475

    Article  CAS  Google Scholar 

  32. Abdallah O, Ghani SA, Hrouzkova S (2017) Development of validated LC-MS/MS method for imidacloprid and acetamiprid in parsley and rocket and evaluation of their dissipation dynamics. J Liq Chromatogr R T 40:392–399

    Article  CAS  Google Scholar 

  33. Yeter O, Aydin A (2014) Determination of acetamiprid and IM-1-2 in postmortem human blood, liver, stomach contents by HPLC-DAD. J Forensic Sci 59:287–292

    Article  CAS  Google Scholar 

  34. Hu W, Chen Q, Li H, Ouyang Q, Zhao J (2016) Fabricating a novel label-free aptasensor for acetamiprid by fluorescence resonance energy transfer between NH2-NaYF4: Yb, ho@SiO2 and Au nanoparticles (vol 80, pg 398, 2016). Biosens Bioelectron 85:997–997

    Article  CAS  Google Scholar 

  35. Liu B, Huang YX, Lian HT, Wu HM (2011) Preparations and characters for acetamiprid of molecular imprinted polymer electrochemical sensors. Electrochemistry 17:323–326

    CAS  Google Scholar 

  36. Rapini R, Cincinelli A, Marrazza G (2016) Acetamiprid multidetection by disposable electrochemical DNA aptasensor. Talanta 161:15–21

    Article  CAS  Google Scholar 

  37. Wanatabe S, Ito S, Kamata Y, Omoda N, Yamazaki T, Munakata H, Kaneko T, Yuasa Y (2001) Development of competitive enzyme-linked immunosorbent assays (ELISAs) based on monoclonal antibodies for chloronicotinoid insecticides imidacloprid and acetamiprid. Anal Chim Acta 427:211–219

    Article  CAS  Google Scholar 

  38. Weerathunge P, Ramanathan R, Shukla R, Sharma TK, Bansal V, Chem A (2014) Aptamer-controlled reversible inhibition of gold nanozyme activity for pesticide sensing. Anal Chem 86:11937–11941

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was partially supported by Jiangsu Agriculture Science and Technology Innovation Fund (CX(18)2025), National Natural Science Fund of China (NSFC 31772086), Jiangsu Planned Projects for Postdoctoral Research Funds (1701097B), Fundamental Research Funds for the Central Universities JUSRP21826, and Young Elite Scientists Sponsorship Program by CAST (2017QNRC001).

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Authors and Affiliations

  1. State Key Laboratory of Food Science and Technology, Jiangnan University, Wuxi, 214122, China

    Qianru Yu, Nuo Duan & Shijia Wu

  2. School of Food Science and Technology, Jiangnan University, Wuxi, 214122, China

    Qianru Yu, Chuxian He, Qian Li, You Zhou, Nuo Duan & Shijia Wu

  3. International Joint Laboratory on Food Safety, Jiangnan University, Wuxi, 214122, China

    Nuo Duan & Shijia Wu

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  1. Qianru Yu
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  2. Chuxian He
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Correspondence to Shijia Wu.

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Yu, Q., He, C., Li, Q. et al. Fluorometric determination of acetamiprid using molecularly imprinted upconversion nanoparticles. Microchim Acta 187, 222 (2020). https://doi.org/10.1007/s00604-020-4204-0

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