Microchimica Acta

, 186:524 | Cite as

Direct molecular imprinting technique to synthesize coated electrospun nanofibers for selective solid-phase microextraction of chlorpyrifos

  • Vajihe Mohammadi
  • Mohammad SarajiEmail author
  • Mohammad Taghi Jafari
Original Paper


Molecularly imprinted-electrospun nanofibers based on the use of poly(vinyl alcohol) were fabricated and used as a new sorbent for solid-phase microextraction of chlorpyrifos. The molecularly imprinted nanofibers were prepared by electrospinning and direct molecular imprinting of polymeric nanofibers. Poly(vinyl alcohol) was used as the functional and electrospun polymer. Chlorpyrifos was used as a template molecule, and glutaraldehyde as the cross-linker. Detection was performed by ion mobility spectrometry equipped with a secondary electrospray ionization source. The molecularly imprinted fiber has a selectivity and extraction efficiency better than the fiber fabricated using the conventional method of encapsulating MIP particles in electrospun nanofibers. Parameters affecting the extraction efficiency such as ionic strength, stirring rate, extraction time, and temperature were evaluated. The dynamic range of the method was in the range of 0.5–200 μg L−1 with the limit of detection of 0.1 μg L−1. The intra- and inter-day relative standard deviations of the method were 4 and 9%, respectively. The fiber-to-fiber reproducibility for three different fibers is 5%. The spiking recoveries from spiked apple, cucumber, and water samples were in the range of 82–112%.

Graphical abstract

Molecularly imprinted-electrospun nanofibers were fabricated based on the direct molecular imprinting technique and used as a new SPME fiber coating for selective extraction of chlorpyrifos from fruits and water samples prior its determination by secondary electrospray ionization-ion mobility spectrometry.


Molecularly imprinted-nanofibers Electrospinning Poly(vinyl alcohol) Ion mobility spectrometry Secondary electrospray ionization Organophosphorus pesticides Well water Agricultural wastewater Fruit samples 



The research council of Isfahan University of Technology (IUT) and the Center of Excellence in Sensor and Green Chemistry are acknowledged for financial support of the project.

Compliance with ethical standards

The authors declare that they have no competing interests.

Supplementary material

604_2019_3641_MOESM1_ESM.docx (699 kb)
ESM 1 (DOCX 698 kb)


  1. 1.
    Bagheri H, Amanzadeh H, Yamini Y et al (2018) A nanocomposite prepared from a zinc-based metal-organic framework and polyethersulfone as a novel coating for the headspace solid-phase microextraction of organophosphorous pesticides. Microchim Acta 185:62CrossRefGoogle Scholar
  2. 2.
    Turiel E, Martín-Esteban A (2009) Molecularly imprinted polymers for solid-phase microextraction. J Sep Sci 32:3278–3284CrossRefGoogle Scholar
  3. 3.
    Sarafraz-Yazdi A, Razavi N (2015) Application of molecularly-imprinted polymers in solid-phase microextraction techniques. Trends Anal Chem 73:81–90CrossRefGoogle Scholar
  4. 4.
    Xu J, Ouyang G (2017) Solid phase microextraction. Springer, Berlin HeidelbergGoogle Scholar
  5. 5.
    Xu P, Xu W, Zhang X, Yan Y (2010) A surface-imprinted polymer for removing dibenzothiophene from gasoline. Microchim Acta 171:441–449CrossRefGoogle Scholar
  6. 6.
    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
  7. 7.
    Xue J, Xie J, Liu W, Xia Y (2017) Electrospun nanofibers: new concepts, materials, and applications. Acc Chem Res 50:1976–1987CrossRefGoogle Scholar
  8. 8.
    Piperno S, Tse Sum Bui B, Haupt K, Gheber LA (2011) Immobilization of molecularly imprinted polymer nanoparticles in electrospun poly(vinyl alcohol) nanofibers. Langmuir 27:1547–1550CrossRefGoogle Scholar
  9. 9.
    Zaidi SA (2015) Recent developments in molecularly imprinted polymer nanofibers and their applications. Anal Methods 7:7406–7415CrossRefGoogle Scholar
  10. 10.
    Ghorani B, Tucker N, Yoshikawa M (2015) Approaches for the assembly of molecularly imprinted electrospun nanofibre membranes and consequent use in selected target recognition. Food Res Int 78:448–464CrossRefGoogle Scholar
  11. 11.
    Isezaki J, Yoshikawa M (2014) Molecularly imprinted nanofiber membranes : localization of molecular recognition sites on the surface of nanofiber. J Memb Separ Tech 3:119–126CrossRefGoogle Scholar
  12. 12.
    Ogunlaja AS, Coombes MJ, Torto N, Tshentu ZR (2014) The adsorptive extraction of oxidized sulfur-containing compounds from fuels by using molecularly imprinted chitosan materials. React Funct Polym 81:61–76CrossRefGoogle Scholar
  13. 13.
    Kim WJ, Chang JY (2011) Molecularly imprinted polyimide nanofibers prepared by electrospinning. Mater Lett 65:1388–1391CrossRefGoogle Scholar
  14. 14.
    Sueyoshi Y, Fukushima C, Yoshikawa M (2010) Molecularly imprinted nanofiber membranes from cellulose acetate aimed for chiral separation. J Membr Sci 357:90–97CrossRefGoogle Scholar
  15. 15.
    Xue X, Lu R, Li Y et al (2018) Molecularly imprinted electrospun nanofibers for adsorption of 2,4-dinitrotoluene in water. Analyst 143:3466–3471Google Scholar
  16. 16.
    Zhang Y, Wei Q, Zhang Q et al (2011) Molecularly imprinted electrospinning polyethersulfone nano-scale fibers for the binding and recognition of bisphenol A. Sep Sci Technol 46:1615–1620CrossRefGoogle Scholar
  17. 17.
    Yoshimatsu K, Ye L, Lindberg J, Chronakis IS (2008) Selective molecular adsorption using electrospun nanofiber affinity membranes. Biosens Bioelectron 23:1208–1215CrossRefGoogle Scholar
  18. 18.
    Iwasaki H, Yoshikawa M (2016) Molecularly imprinted polyacrylonitrile adsorbents for the capture of Cs + ions. Polym J 48:1151–1156CrossRefGoogle Scholar
  19. 19.
    Ruggieri F, D’Archivio AA, Di Camillo D et al (2015) Development of molecularly imprinted polymeric nanofibers by electrospinning and applications to pesticide adsorption. J Sep Sci 38:1402–1410CrossRefGoogle Scholar
  20. 20.
    Mehrani Z, Ebrahimzadeh H, Aliakbar AR, Asgharinezhad AA (2018) A poly(4-nitroaniline)/poly(vinyl alcohol) electrospun nanofiber as an efficient nanosorbent for solid phase microextraction of diazinon and chlorpyrifos from water and juice samples. Microchim Acta 185:1–9CrossRefGoogle Scholar
  21. 21.
    Jafari MT, Saraji M, Kermani M (2018) Sol-gel electrospinning preparation of hybrid carbon silica nanofibers for extracting organophosphorus pesticides prior to analyzing them by gas chromatography-ion mobility spectrometry. J Chromatogr A 1558:1–13CrossRefGoogle Scholar
  22. 22.
    Ma J-K, Huang XC, Wei S-L (2018) Preparation and application of chlorpyrifos molecularly imprinted solid-phase microextraction probes for the residual determination of organophosphorous pesticides in fresh and dry foods. J Sep Sci 41:3152–3162CrossRefGoogle Scholar
  23. 23.
    Sanagi MM, Salleh S, Ibrahim WAW et al (2013) Molecularly imprinted polymer solid-phase extraction for the analysis of organophosphorus pesticides in fruit samples. J Food Compos Anal 32:155–161CrossRefGoogle Scholar
  24. 24.
    Farajzadeh MA, Mohebbi A (2018) Development of magnetic dispersive solid phase extraction using toner powder as an efficient and economic sorbent in combination with dispersive liquid–liquid microextraction for extraction of some widely used pesticides in fruit juices. J Chromatogr A 1532:10–19CrossRefGoogle Scholar
  25. 25.
    Jafari Horestani AR, Jafari MT, Jazan E, Mossaddegh M (2018) Effect of halide ions on secondary electrospray ionization-ion mobility spectrometry for the determination of TNT extracted by dispersive liquid-liquid microextraction. Int J Mass Spectrom 433:19–24CrossRefGoogle Scholar
  26. 26.
    Rudra R, Kumar V, Kundu PP (2015) Acid catalysed cross-linking of poly(vinyl alcohol) (PVA) by glutaraldehyde: effect of crosslink density on the characteristics of PVA membranes used in single chambered microbial fuel cells. RSC Adv 5:83436–83447CrossRefGoogle Scholar
  27. 27.
    Yang C-C (2011) Fabrication and characterization of poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) proton-conducting composite membranes for direct methanol fuel cells. Int J Hydrog Energy 36:4419–4431CrossRefGoogle Scholar
  28. 28.
    Spivak DA (2005) Optimization, evaluation, and characterization of molecularly imprinted polymers. Adv Drug Deliv Rev 57:1779–1794CrossRefGoogle Scholar
  29. 29.
    Ellwanger A, Berggren C, Bayoudh S, Crecenzi C, Karlsson L, Owens PK, Ensing K, Cormack P, Sherrington D, Sellergren B (2001) Evaluation of methods aimed at complete removal of template from molecularly imprinted polymers. Analyst 126:784–792CrossRefGoogle Scholar
  30. 30.
    Piri-Moghadam H, Gionfriddo E, Rodriguez-Lafuente A et al (2017) Inter-laboratory validation of a thin film microextraction technique for determination of pesticides in surface water samples. Anal Chim Acta 964:74–84CrossRefGoogle Scholar
  31. 31.
    Bahrami H, Rezaei B, Jafari MT (2019) Coupling of a novel electrospun polyacrylonitrile/amino-Zr-MOF nanofiber as a thin film for microextraction-corona discharge-ion mobility spectrometry for the analysis of chlorpyrifos in water samples. Anal Methods 11:1073–1079CrossRefGoogle Scholar
  32. 32.
    Rodrigues F d M, Mesquita PRR, Oliveira LS et al (2011) Development of a headspace solid-phase microextraction/gas chromatography-mass spectrometry method for determination of organophosphorus pesticide residues in cow milk. Microchem J 98:56–61CrossRefGoogle 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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