Skip to main content
Log in

Novel molecularly imprinted polymeric microspheres for preconcentration and preservation of polycyclic aromatic hydrocarbons from environmental samples

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Molecularly imprinted polymer (MIP) microspheres with diameters in the range 60–500 μm were synthesized in a continuous segmented flow microfluidic reactor and used as packing material for microtraps for the selective separation of benzo[a]pyrene (BAP) from environmental aqueous samples. The synthesis involved the pumping of monodisperse droplets of acetonitrile containing methacrylic acid as the functional monomer, BAP as a template, and ethylene glycol dimethacrylate as the cross-linking monomer into the microchannels of the microfluidic reactor. The microspheres showed high adsorption capacity and selectivity for BAP in aqueous solutions; both are important for the environmental monitoring and analysis of BAP. The adsorption capacity for BAP of the smallest MIP microspheres (size range 60–80 μm), prepared as part of this study, was 75 mg g-1 in aqueous solutions; furthermore, this adsorption capacity was close to 300 % higher than that of commercially used activated carbon. Microtraps packed with MIP retained BAP intact for at least 30 days, whereas microtraps packed with activated carbon for BAP showed 40 % reduction in BAP concentration for the same period. This study has demonstrated that MIP microtraps have significant potential for the selective enrichment and preservation of targeted polycyclic aromatic hydrocarbons from complex environmental samples.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Afghan BK, Chau ASY (1989) Analysis of trace organics in the aquatic environment. CRC, Boca Raton

    Google Scholar 

  2. Bostrom C, Gerde P, Hanberg A, Jernstrom B, Johanson C, Kyrkland T, Rannug A, Tornquist M, Vicotrin K, Westerholm R (2002) Cancer risk assessment, indicators, and guidelines for polycyclic aromatic hydrocarbons in the ambient air. Environ Health Perspect 110:451–466

    Article  CAS  Google Scholar 

  3. Arey J (1998) In: Nielson AH (ed) PAHs and related compounds. Handbook of environmental chemistry, vol 3. Springer, Berlin

    Google Scholar 

  4. US Environmental Protection Agency (1984) Guidelines establishing test procedures for analysis of pollutants. 40 CFT. 135, 1-120. Fed Regist

  5. European Parliament Council (2001) Decision No 2455/2001/EC of the European Parliament and of the Council of 20 November 2001 establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC (text with EEA relevance). Off J Eur Communities L 331:1–5

    Google Scholar 

  6. Lopez-Avila L (1999) Sample preparation for environmental analysis. Crit Rev Anal Chem 29:195–230

    Article  CAS  Google Scholar 

  7. Pawliszyn J, Pedersen-Bjergaard S (2005) Analytical microextraction: current status and future trends. J Chromatogr Sci 44:291–307

    Article  Google Scholar 

  8. de Fatima Alpendurada M (2000) Solid-phase microextraction: a promising technique for sample preparation in environmental analysis. J Chromatogr A 889:3–14

    Article  Google Scholar 

  9. Kostopoulou K, Nikolaou A (2008) Analytical problems and the need for sample preparation in the determination of pharmaceuticals and their metabolites in aqueous environmental matrices. Trends Anal Chem 27:1023–1035

    Article  CAS  Google Scholar 

  10. Wulff G, Sarhan A (1972) Use of polymers with enzyme-analogous structures for the resolution of racemates. Angew Chem Int Ed 11:341–345

    CAS  Google Scholar 

  11. Mayes AG, Mosbach K (1997) Molecularly imprinted polymers: useful materials for analytical chemistry? Trends Anal Chem 16:321–332

    Article  CAS  Google Scholar 

  12. Sellergren B (2000) Imprinted polymers with memory for small molecules, proteins, or crystals. Angew Chem Int Ed 39:1031–1037

    Article  CAS  Google Scholar 

  13. Spivak D, Simon R, Campbell J (2004) Evidence for shape selectivity in non-covalently imprinted polymers. Anal Chim Acta 504:23–30

    Article  CAS  Google Scholar 

  14. Dai S, Burleigh MC, Ju YH, Gao HJ, Lin JS, Pennycook SJ, Barnes CE, Xue ZL (2000) Hierarchically imprinted sorbents for the separation of metal ions. J Am Chem Soc 122:992–993

    Article  CAS  Google Scholar 

  15. Rao TP, Kala R, Daniel S (2006) Metal ion imprinted polymers—novel materials for selective recognition of inorganics. Anal Chim Acta 578:105–111

    Article  CAS  Google Scholar 

  16. Zhao WF, Fang BH, Li N, Nie SQ, Wei Q, Zhao CS (2009) Fabrication of pH-responsive molecularly imprinted polyethersulfone particles for bisphenol-A uptake. J Appl Polym Sci 113:916–921

    Article  CAS  Google Scholar 

  17. Chen L, Xu S, Li J (2011) Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev 40:2922–2942

    Article  CAS  Google Scholar 

  18. Krupadam RJ, Bhagat B, Wate SR, Bodhe GL, Sellergren B, Anjaneyulu Y (2009) Fluorescence spectrophotometer analysis of polycyclic aromatic hydrocarbons in environmental samples based on solid Phase extraction using molecularly imprinted polymer. Environ Sci Technol 43:2871–2877

    Article  CAS  Google Scholar 

  19. Krupadam RJ, Khan MS, Wate SR (2010) Removal of probable human carcinogenic polycyclic aromatic hydrocarbons from contaminated water using molecularly imprinted polymer. Water Res 44:681–688

    Article  CAS  Google Scholar 

  20. Krupadam RJ, Bhagat B, Khan MS (2010) Highly sensitive determination of polycyclic aromatic hydrocarbons in ambient air dust by gas chromatography-mass spectrometry after molecularly imprinted polymer extraction. Anal Bioanal Chem 397:3097–3106

    Article  CAS  Google Scholar 

  21. Krupadam RJ (2011) An efficient fluorescent polymer sensing material for detection of traces of benzo[α]pyrene in environmental samples. Environ Chem Lett 9:389–395

    Article  CAS  Google Scholar 

  22. Song X, Li J, Xu S, Ying R, Ma J, Liao C, Liu D, Yu J, Chen L (2012) Determination of 16 polycyclic aromatic hydrocarbons in seawater using molecularly imprinted solid-phase extraction coupled with gas chromatography-mass spectrometry. Talanta 99:75–82

    Article  CAS  Google Scholar 

  23. Sellergren B, Andersson L (1990) Molecular recognition in macroporous polymers prepared by substrate analog imprinting strategy. J Org Chem 55:3381–3383

    Article  CAS  Google Scholar 

  24. Rockne KJ, Strand SE (1998) Biodegradation of bicyclic and polycyclic aromatic hydrocarbons in anaerobic enrichments. Environ Sci Technol 32:3962–3967

    Article  CAS  Google Scholar 

  25. Zhu QZ, Haupt K, Knopp D, Neissner R (2002) Molecularly imprinted polymer for metsulfuron-methyl and its binding characteristics for sulfonylurea herbicides. Anal Chim Acta 468:217–227

    Article  CAS  Google Scholar 

  26. Bomchil G, Herino R, Barla K, Pfister JC (1983) Pore size distribution in porous silicon studied by adsorption isotherms. J Electrochem Soc 130:1611–1614

    Article  CAS  Google Scholar 

  27. Krupadam RJ, Ahuja R, Wate SR (2007) Benzo(α)pyrene imprinted polyacrylate nanosurfaces: Adsorption and binding characteristics. Sens Actuators B 124:444–451

    Article  CAS  Google Scholar 

  28. Pichon V, Chapuis-Hugon F (2008) Role of molecularly imprinted polymers for selective determination of environmental pollutants—a review. Anal Chim Acta 622:48–61

    Article  CAS  Google Scholar 

  29. Turner NW, Piletska EV, Karim K, Whitcombe M, Malecha M, Magan N, Baggiani C, Piletsky SA (2004) Effects of the solvent on recognition properties of molecularly imprinted polymer specific for ochratoxin A. Biosens Bioelectron 20:1060–1067

    Article  CAS  Google Scholar 

  30. Ye L, Yu Y, Mosbach K (2000) Towards the development of molecularly imprinted artificial receptors for the screening of estrogenic chemicals. Analyst 126:760–765

    Article  Google Scholar 

  31. Ariza JLG, Morales E, Sanchez-Rodas D, Giraldez I (2000) Stability of chemical species in environmental matrices. Trends Anal Chem 19:200–209

    Article  CAS  Google Scholar 

  32. McSheehy S, Szpunar J, Morabito R, Quevauviller PH (2003) The speciation of arsenic in biological tissues and the certification of reference materials for quality control. Trends Anal Chem 22:191–209

    Article  CAS  Google Scholar 

  33. Hadjiev D, Dimitrov D, Martinov M, Sire O (2007) Enhancement of the biofilm formation on polymeric supports by surface conditioning. Enzyme Microbial Technol 40:840–848

    Article  CAS  Google Scholar 

  34. Saiz-Jimenez C (1997) Biodeterioration vs biodegradation: the role of microorganisms in the removal of pollutants deposited on historic buildings. Int J Biodeter Biodegrad 40:225–232

    Article  CAS  Google Scholar 

  35. Gomes S, Nogueira R, Oliveira JM, Peixoto P, Brito AG (2009) Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM. Environ Sci Pollut Res 16:671–678

    Article  CAS  Google Scholar 

Download references

Acknowledgments

R.J.K acknowledges financial support from the Council of Scientific and Industrial Research, New Delhi, and the Planning Commission, Government of India, under the Molecular Environmental Science and Engineering Research program.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Reddithota J. Krupadam.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Krupadam, R.J., Korde, B.A., Ashokkumar, M. et al. Novel molecularly imprinted polymeric microspheres for preconcentration and preservation of polycyclic aromatic hydrocarbons from environmental samples. Anal Bioanal Chem 406, 5313–5321 (2014). https://doi.org/10.1007/s00216-014-7952-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-014-7952-z

Keywords

Navigation