Microchimica Acta

, 186:396 | Cite as

Molecularly imprinted graphite spray ionization-ion mobility spectrometry: application to trace analysis of the pesticide propoxur

  • Tahereh Zargar
  • Mohammad T. JafariEmail author
  • Taghi KhayamianEmail author
Original Paper


A porous graphite sheet modified by a molecularly imprinted polymer (MIP) was directly used as the spray ionization source for ion mobility spectrometry (IMS). Therefore, it was possible to selectively analyze samples extracted by the molecularly imprinted polymer. This obviates the need for the steps of elution, solvent evaporation, dissolution and injection. To prepare the sheet, the graphite surface was first modified by electrodeposition of a molecularly imprinted polypyrrole film. This polypyrrole film was fabricated in a three-electrode electrochemical system using cyclic voltammetry. The electropolymerization of the graphite sheet was carried out with LiClO4 as a supporting electrolyte in the reaction solution. The effects of the amount of monomer, the level of template concentrations, and the time of polymerization on the extraction efficiency of the MIP film were evaluated. The extraction conditions including extraction time, the extraction temperature, the pH values, the salt concentrations, and the stirring rate were also studied. Methanol was selected as the most suitable solvent for both desorption and ionization which occur simultaneously. The pesticide propoxur (acting as a test compound) was extracted from water samples and directly analyzed using IMS. The analytical parameters (working range: 1.0 to 250 ng·mL−1; detection limit: 0.3 ng·mL−1) indicated that the direct coupling of MIP and IMS has a great potential in terms of reproducibility, and speed of the analysis, while maintaining acceptable sensitivity.

Graphical abstract

Schematic presentation of molecularly imprinted graphite spray ionization coupled with ion mobility spectrometry (IMS) for rapid/selective extraction and ionization: Application to the pre-concentration of propoxur prior to its quantification by IMS.


MIP separation Electropolymerization Modified graphite sheet Spray ionization IMS technique Pesticide Thin film micro-extraction 



The Research Community of Isfahan University of Technology (IUT) and Excellence Center in Sensor and Green Chemistry are highly appreciated for providing the financial support of this work.

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3467_MOESM1_ESM.docx (98 kb)
ESM 1 (DOCX 98.4 kb)


  1. 1.
    Eiceman GA, Karpas Z, Hill Jr HH (2016) Ion mobility spectrometry. Third ed. CRC Press, Taylor & Franμcis GroupGoogle Scholar
  2. 2.
    Shumate C (1994) Electrospray ion mobility spectrometry. TrAC Trends Anal Chem 13:104–109CrossRefGoogle Scholar
  3. 3.
    Wittmer D, Chen YH, Luckenbill BK, Hill HH (1994) Electrospray ionization ion mobility spectrometry. Anal Chem 66:2348–2355CrossRefGoogle Scholar
  4. 4.
    Wu C, Siems WF, Hill HH (2000) Secondary electrospray ionization ion mobility spectrometry/mass spectrometry of illicit drugs. Anal Chem 72:396–403CrossRefGoogle Scholar
  5. 5.
    Tam M, Hill HH (2004) Secondary electrospray ionization-ion mobility spectrometry for explosive vapor detection. Anal Chem 76:2741–2747CrossRefGoogle Scholar
  6. 6.
    Weston DJ, Bateman R, Wilson ID, Wood TR, Creaser CS (2005) Direct analysis of pharmaceutical drug formulations using ion mobility spectrometry/quadrupole-time-of-flight mass spectrometry combined with desorption electrospray ionization. Anal Chem 77:7572–7580CrossRefGoogle Scholar
  7. 7.
    Myung S, Wiseman JM, Valentine SJ, Takats Z, Cooks RG, Clemmer DE (2006) Coupling desorption electrospray ionization with ion mobility/mass spectrometry for analysis of protein structure: evidence for desorption of folded and denatured states. J Phys Chem B 110:5045–5051CrossRefGoogle Scholar
  8. 8.
    Wang H, Liu J, Cooks RG, Ouyang Z (2010) Paper spray for direct analysis of complex mixtures using mass spectrometry. Angew Chem 122:889–892CrossRefGoogle Scholar
  9. 9.
    Wu MX, Wang HY, Zhang JT, Guo YL (2016) Multifunctional carbon fiber ionization mass spectrometry. Anal Chem 88:9547–9553CrossRefGoogle Scholar
  10. 10.
    Zargar T, Jafari MT, Khayamian T (2018) Porous graphite sheet spray ionization ion mobility spectrometry. J Mass Spectrom 53:1135–1142CrossRefGoogle Scholar
  11. 11.
    Hu B, So PK, Chen HW, Yao ZP (2011) Electrospray ionization using wooden tips. Anal Chem 83:8201–8207CrossRefGoogle Scholar
  12. 12.
    Liu J, Wang H, Cooks RG, Ouyang Z (2011) Leaf spray: direct chemical analysis of plant material and living plants by mass spectrometry. Anal Chem 83:7608–7613CrossRefGoogle Scholar
  13. 13.
    Jeng J, Shiea J (2003) Electrospray ionization from a droplet deposited on a surface-modified glass rod. Rapid Commun Mass Spectrom 17:1709–1713CrossRefGoogle Scholar
  14. 14.
    Gómez-Ríos GA, Pawliszyn J (2014) Development of coated blade spray ionization mass spectrometry for the quantitation of target analytes present in complex matrices. Angew Chem Int Ed 53:14503–14507CrossRefGoogle Scholar
  15. 15.
    Li T, Fan L, Wang Y, Huang X, Xu J, Lu J, Zhang M, Xu W (2017) Molecularly imprinted membrane electrospray ionization for direct sample analyses. Anal Chem 89:1453–1458CrossRefGoogle Scholar
  16. 16.
    Deng J, Yu T, Yao Y, Peng Q, Luo L, Chen B, Wang X, Yang Y, Luan T (2017) Surface-coated wooden-tip electrospray ionization mass spectrometry for determination of trace fluoroquinolone and macrolide antibiotics in water. Anal Chim Acta 954:52–59CrossRefGoogle Scholar
  17. 17.
    Zhang Z, Xu W, Manicke NE, Cooks RG, Ouyang Z (2011) Silica coated paper substrate for paper-spray analysis of therapeutic drugs in dried blood spots. Anal Chem 84:931–938CrossRefGoogle Scholar
  18. 18.
    Han F, Yang Y, Ouyang J, Na N (2015) Direct analysis of in-gel proteins by carbon nanotubes-modified paper spray ambient mass spectrometry. Analyst 140:710–715CrossRefGoogle Scholar
  19. 19.
    Liu J, He Y, Chen S, Ma M, Yao S, Chen B (2017) New urea-modified paper substrate for enhanced analytical performance of negative ion mode paper spray mass spectrometry. Talanta 166:306–314CrossRefGoogle Scholar
  20. 20.
    Zargar T, Khayamian T, Jafari MT (2017) Immobilized aptamer paper spray ionization source for ion mobility spectrometry. J Pharm Biomed Anal 132:232–237CrossRefGoogle Scholar
  21. 21.
    Zargar T, Khayamian T, Jafari MT (2018) Aptamer-modified carbon nanomaterial based sorption coupled to paper spray ion mobility spectrometry for highly sensitive and selective determination of methamphetamine. Microchim Acta 185:103CrossRefGoogle Scholar
  22. 22.
    Tavares LS, Carvalho TC, Romão W, Vaz BG, Chaves AR (2018) Paper spray tandem mass spectrometry based on molecularly imprinted polymer substrate for cocaine analysis in Oral fluid. J Am Soc Mass Spectrom 29:566–572CrossRefGoogle Scholar
  23. 23.
    Lerma-García MJ, Zougagh M, Ríos A (2013) Magnetic molecular imprint-based extraction of sulfonylurea herbicides and their determination by capillary liquid chromatography. Microchim Acta 180:363–370CrossRefGoogle Scholar
  24. 24.
    Sorribes-Soriano A, de la Guardia M, Esteve-Turrillas FA, Armenta S (2018) Trace analysis by ion mobility spectrometry: from conventional to smart sample preconcentration methods. A review. Anal Chim Acta 1026:37–50CrossRefGoogle Scholar
  25. 25.
    Xie C, Gao S, Guo Q, Xu K (2010) Electrochemical sensor for 2, 4-dichlorophenoxy acetic acid using molecularly imprinted polypyrrole membrane as recognition element. Microchim Acta 169:145–152CrossRefGoogle Scholar
  26. 26.
    Kawaguchi M, Hayatsu Y, Nakata H, Ishii Y, Ito R, Saito K, Nakazawa H (2005) Molecularly imprinted solid phase extraction using stable isotope labeled compounds as template and liquid chromatography–mass spectrometry for trace analysis of bisphenol a in water sample. Anal Chim Acta 539:83–89CrossRefGoogle Scholar
  27. 27.
    Donato FF, Bandeira NM, dos Santos GC, Prestes OD, Adaime MB, Zanella RJ (2017) Evaluation of the rotating disk sorptive extraction technique with polymeric sorbent for multiresidue determination of pesticides in water by ultra-high-performance liquid chromatography–tandem mass spectrometry. J Chromatogr A 1516:54–63CrossRefGoogle Scholar
  28. 28.
    Pebdani AA, Khodadoust S, Toori MA, Zarezade V, Talebianpoor MS (2016) Application of an optimized modified stir bar with ZnS nanoparticles loaded on activated carbon for preconcentration of carbofuran and propoxur insecticides in water samples and their HPLC determination. RSC Adv 6:36238–36247CrossRefGoogle Scholar
  29. 29.
    El-Sheikh AH, Insisi AA, Sweileh JA (2007) Effect of oxidation and dimensions of multi-walled carbon nanotubes on solid phase extraction and enrichment of some pesticides from environmental waters prior to their simultaneous determination by high performance liquid chromatography. J Chromatogr A 1164:25–32CrossRefGoogle Scholar
  30. 30.
    Wu J, Xiang B, Xia J (2009) Application of ultrasound-assisted emulsification-microextraction combined with high performance liquid chromatography to the determination of propoxur in environmental and beverage samples. Microchim Acta 166:157–162CrossRefGoogle Scholar
  31. 31.
    Bogialli S, Curini R, Di Corcia A, Laganà A, Nazzari M, Tonci M (2004) Simple and rapid assay for analyzing residues of carbamate insecticides in bovine milk: hot water extraction followed by liquid chromatography–mass spectrometry. J Chromatogr A 1054:351–357CrossRefGoogle Scholar
  32. 32.
    Selva TMG, Paixão TRLC (2016) Electrochemical quantification of propoxur using a boron-doped diamond electrode. Diam Relat Mater 66:113–118CrossRefGoogle Scholar
  33. 33.
    Qader B, Baron M, Hussain I, Gonzalez-Rodriguez J (2018) Electrochemical determination of 2-isopropoxyphenol in glassy carbon and molecularly imprinted poly-pyrrole electrodes. J Electroanal Chem 821:16–21CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryIsfahan University of TechnologyIsfahanIran

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