Skip to main content
Log in

Water compatible molecularly imprinted nanoparticles as a restricted access material for extraction of hippuric acid, a biological indicator of toluene exposure, from human urine

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

The authors describe the preparation of molecularly imprinted nanoparticles (MINPs) for the solid phase extraction of hippuric acid (HA). The MINPs consists of a water-compatible organic-inorganic silica composite which was obtained from a functionalized silica by the sol-gel method. HA acted as the template, 3-aminopropyl trimethoxysilane as the functional monomer, and tetraethoxysilane as the crosslinker. Subsequently, methacryloxypropyltrimethoxysilane was used as a coupling agent to deposit a hydrophilic acrylamide coating onto the surface of the MINPs. The morphology and structure of the resulting restricted access material (referred to as RAM-MINP) were characterized by scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. Solid phase extraction of HA was accomplished by passing urine samples through a RAM-MINP-packed SPE cartridge. Following elution, HA was quantified by HPLC using UV detection at 228 nm. The effects of sample pH, amount of sorbent and eluent and washing solvent volumes were optimized by experimental design methodology under response surface methodology. Under optimized conditions, the mean extraction efficiency of HA from spiked samples is adequately repeatable, with relative standard deviations of <6.1%. The limits of detection and quantitation are 0.15 and 0.25 μg.L−1, respectively.

Schematic of the the preparation of molecularly imprinted nanoparticles (MINP) for the solid phase extraction of hippuric acid (HA). Solid phase extraction of HA was accomplished by passing urine samples through a RAM-MINP-packed SPE cartridge. After solid phase extraction and elution, HA was quantified by HPLC using UV detection at 228 nm.

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.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Boor JW, Hurtig HI (1977) Persistent cerebellar ataxia after exposure to toluene. Ann Neurol 2(5):440–442

    Article  CAS  Google Scholar 

  2. Rosenberg NL, Spitz MC, Filley CM, Davis KA, Schaumburg HH (1988) Central nervous system effects of chronic toluene abuse—clinical, brainstem evoked response and magnetic resonance imaging studies. Neurotoxicol Teratol 10(5):489–495

    Article  CAS  Google Scholar 

  3. Feldman RG, Ratner MH, Ptak T (1999) Chronic toxic encephalopathy in a painter exposed to mixed solvents. Environ Health Perspect 107(5):417–422

    Article  CAS  Google Scholar 

  4. Berenguer P, Soulage C, Perrin D, Pequignot J-M, Abraini JH (2003) Behavioral and neurochemical effects induced by subchronic exposure to 40 ppm toluene in rats. Pharmacol Biochem Behav 74(4):997–1003

    Article  CAS  Google Scholar 

  5. Chouanière D, Wild P, Fontana JM, Héry M, Fournier M, Baudin V, Subra I, Rousselle D, Toamain JP, Saurin S (2002) Neurobehavioral disturbances arising from occupational toluene exposure. Am J Ind Med 41(2):77–88

    Article  Google Scholar 

  6. Pierce CH, Chen Y, Dills RL, Kalman DA, Morgan MS (2002) Toluene metabolites as biological indicators of exposure. Toxicol Lett 129(1):65–76

    Article  CAS  Google Scholar 

  7. Wiwanitkit V, Suwansaksri J, Soogarun S (2008) High urine hippuric acid level among police working close to traffic in an urban area, Thailand: a preliminary study. Stoch Env Res Risk A 22(2):281–283

    Article  Google Scholar 

  8. Inoue N, Ooya T, Takeuchi T (2014) Erratum to: hydrophilic molecularly imprinted polymers for bisphenol a prepared in aqueous solution. Microchim Acta 181(15–16):2009–2009

    Article  CAS  Google Scholar 

  9. Wang Y-Z, Li D-Y, He X-W, Li W-Y, Zhang Y-K (2015) Epitope imprinted polymer nanoparticles containing fluorescent quantum dots for specific recognition of human serum albumin. Microchim Acta 182(7–8):1465–1472

    Article  CAS  Google Scholar 

  10. Wei X, Zhou Z, Hao T, Xu Y, Li H, Lu K, Dai J, Zheng X, Gao L, Wang J (2015) Specific recognition and fluorescent determination of aspirin by using core-shell CdTe quantum dot-imprinted polymers. Microchim Acta 182(7–8):1527–1534

    Article  CAS  Google Scholar 

  11. Bates F, del Valle M (2015) Voltammetric sensor for theophylline using sol–gel immobilized molecularly imprinted polymer particles. Microchim Acta 182(5–6):933–942

    Article  CAS  Google Scholar 

  12. Tan L, He R, Chen K, Peng R, Huang C, Yang R, Tang Y (2016) Ultra-high performance liquid chromatography combined with mass spectrometry for determination of aflatoxins using dummy molecularly imprinted polymers deposited on silica-coated magnetic nanoparticles. Microchim Acta 183(4):1469–1477

    Article  CAS  Google Scholar 

  13. Li S, Wu X, Zhang Q, Li P (2016) Synergetic dual recognition and separation of the fungicide carbendazim by using magnetic nanoparticles carrying a molecularly imprinted polymer and immobilized β-cyclodextrin. Microchim Acta 183(4):1433–1439

    Article  CAS  Google Scholar 

  14. Yang G, He Z, Liu X, Liu C, Zhan J, Liu D, Wang P, Zhou Z (2016) Polymer-coated magnetic nanospheres for preconcentration of organochlorine and pyrethroid pesticides prior to their determination by gas chromatography with electron capture detection. Microchim Acta 183(3):1187–1194

    Article  CAS  Google Scholar 

  15. Li L, Lin Z-z, X-m C, H-y Z, Lin Y-d, Z-z L, Z-y H (2015) Molecularly imprinted polymers for extraction of malachite green from fish samples prior to its determination by HPLC. Microchim Acta 182(9–10):1791–1796

    Article  CAS  Google Scholar 

  16. Bures P, Huang Y, Oral E, Peppas NA (2001) Surface modifications and molecular imprinting of polymers in medical and pharmaceutical applications. J Control Release 72(1):25–33

    Article  CAS  Google Scholar 

  17. Du B, Qu T, Chen Z, Cao X, Han S, Shen G, Wang L (2014) A novel restricted access material combined to molecularly imprinted polymers for selective solid-phase extraction and high performance liquid chromatography determination of 2-methoxyestradiol in plasma samples. Talanta 129:465–472

    Article  CAS  Google Scholar 

  18. He J, Song L, Chen S, Li Y, Wei H, Zhao D, Gu K, Zhang S (2015) Novel restricted access materials combined to molecularly imprinted polymers for selective solid-phase extraction of organophosphorus pesticides from honey. Food Chem 187:331–337

    Article  CAS  Google Scholar 

  19. Santos MG, Moraes GOI, Nakamura MG, dos Santos-Neto ÁJ, Figueiredo EC (2015) Restricted access molecularly imprinted polymers obtained by bovine serum albumin and/or hydrophilic monomers’ external layers: a comparison related to physical and chemical properties. Analyst 140(22):7768–7775

    Article  CAS  Google Scholar 

  20. Souza ID, Melo LP, Jardim IC, Monteiro JC, Nakano AMS, Queiroz MEC (2016) Selective molecularly imprinted polymer combined with restricted access material for in-tube SPME/UHPLC-MS/MS of parabens in breast milk samples. Anal Chim Acta 932:49–59

    Article  CAS  Google Scholar 

  21. Moraes GOI, da Silva LMR, dos Santos-Neto ÁJ, Florenzano FH, Figueiredo EC (2013) A new restricted access molecularly imprinted polymer capped with albumin for direct extraction of drugs from biological matrices: the case of chlorpromazine in human plasma. Anal Bioanal Chem 405(24):7687–7696

    Article  CAS  Google Scholar 

  22. Sambe H, Hoshina K, Haginaka J (2007) Molecularly imprinted polymers for triazine herbicides prepared by multi-step swelling and polymerization method: their application to the determination of methylthiotriazine herbicides in river water. J Chromatogr A 1152(1):130–137

    Article  CAS  Google Scholar 

  23. Manesiotis P, Borrelli C, Aureliano CS, Svensson C, Sellergren B (2009) Water-compatible imprinted polymers for selective depletion of riboflavine from beverages. J Mater Chem 19(34):6185–6193

    Article  CAS  Google Scholar 

  24. Arabi M, Ghaedi M, Ostovan A (2016) Development of dummy molecularly imprinted based on functionalized silica nanoparticles for determination of acrylamide in processed food by matrix solid phase dispersion. Food Chem 210:78–84

    Article  CAS  Google Scholar 

  25. Zhu R, Zhao W, Zhai M, Wei F, Cai Z, Na Sheng QH (2010) Molecularly imprinted layer-coated silica nanoparticles for selective solid-phase extraction of bisphenol a from chemical cleansing and cosmetics samples. Anal Chim Acta 658:209–216

    Article  CAS  Google Scholar 

  26. Atakay M, Omr ÇÇ, Salih B (2012) Amine-functionalized sol–gel-based lab-in-a-pipet-tip approach for the fast enrichment and specific purification of phosphopeptides in MALDI-MS applications. Anal Chem 84(6):2713–2720

    Article  CAS  Google Scholar 

  27. da Costa Silva RG, Augusto F (2006) Sol–gel molecular imprinted ormosil for solid-phase extraction of methylxanthines. J Chromatogr A 1114(2):216–223

    Article  Google Scholar 

  28. Mehdinia A, Kayyal TB, Jabbari A, Ovais M, Aziz-Zanjani ZE (2013) Magnetic molecularly imprinted nanoparticles based on grafting polymerization for selective detection of 4-nitrophenol in aqueous samples. J Chromatogr A 1283:82–88

    Article  CAS  Google Scholar 

  29. Ebrahimzadeh H, Dehghani Z, Asgharinezhad AA, Shekari N, Molaei K (2013) Determination of haloperidol in biological samples using molecular imprinted polymer nanoparticles followed by HPLC-DAD detection. Int J Pharm 453(2):601–609

    Article  CAS  Google Scholar 

  30. Arabi M, Ostovan A, Ghaedi M, Purkait MK (2016) Novel strategy for synthesis of magnetic dummy molecularly imprinted nanoparticles based on functionalized silica as an efficient sorbent for the determination of acrylamide in potato chips: optimization by experimental design methodology. Talanta 154:526–532. doi:10.1016/j.talanta.2016.04.010

    Article  CAS  Google Scholar 

  31. Committee AM (1987) Recommendations for the definition, estimation and use of the detection limit. Analyst 112(2):199–204

    Article  Google Scholar 

  32. Toulabi P, Daneshfar A, Sahrai R (2010) Determination of hippuric acid in biological fluids using single drop liquid–liquid-liquid microextraction. Anal Methods 2(5):564–569

    Article  CAS  Google Scholar 

  33. Penner N, Ramanathan R, Zgoda-Pols J, Chowdhury S (2010) Quantitative determination of hippuric and benzoic acids in urine by LC–MS/MS using surrogate standards. J Pharm Biomed Anal 52(4):534–543

    Article  CAS  Google Scholar 

  34. Ohashi Y, Mamiya T, Mitani K, Wang B, Takigawa T, Kira S, Kataoka H (2006) Simultaneous determination of urinary hippuric acid, o-, m-and p-methylhippuric acids, mandelic acid and phenylglyoxylic acid for biomonitoring of volatile organic compounds by gas chromatography–mass spectrometry. Anal Chim Acta 566(2):167–171

    Article  CAS  Google Scholar 

  35. Zinalibdin MR, Yacob AR, Sanagi MM (2015) A novel molecularly imprinted acrylonitrile-butadiene-styrene membrane for adsorption of hippuric acid. Procedia Chem 16:91–98

    Article  CAS  Google Scholar 

  36. Ahmadi F, Asgharloo H, Sadeghi S, Gharehbagh-Aghababa V, Adibi H (2009) Post-derivatization procedure for determination of hippuric acid after extraction by an automated micro solid phase extraction system and monitoring by gas chromatography. J Chromatogr B 877(27):2945–2951

    Article  CAS  Google Scholar 

  37. Wang JZ, Lu XY, Zhao NP, Cheng YY, Zeng S (2007) Simultaneous determination of phenylglyoxylic acid, mandelic acid, styrene glycol and hippuric acid in primary culture of rat hepatocytes incubate by high-performance liquid chromatography. Biomed Chromatogr 21(5):497–501

    Article  CAS  Google Scholar 

  38. Zuppi C, Rossetti DV, Vitali A, Vincenzoni F, Giardina B, Castagnola M, Messana I (2003) Determination of urinary hippuric acid by micellar electrokinetic capillary chromatography. J Chromatogr B 793(2):223–228

    Article  CAS  Google Scholar 

  39. Choi Y-B, Kim N-H, Kim S-H, Tae G-S, Kim H-H (2014) Heterogeneous electrochemical immunoassay of hippuric acid on the electrodeposited organic films. Sensors 14(10):18886–18897

    Article  CAS  Google Scholar 

  40. Jeon WY, Choi YB, Kim HH (2013) Homogeneous electrochemical detection of hippuric acid in urine based on the osmium–antigen conjugate. Chem Phys Chem 14(10):2331–2337

    CAS  Google Scholar 

  41. Hao J-N, Yan B (2015) Recyclable lanthanide-functionalized MOF hybrids to determine hippuric acid in urine as a biological index of toluene exposure. Chem Commun 51(77):14509–14512

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors express their appreciation to the Graduate School and Research Council of Yasouj University for their financial support of this work.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Mehrorang Ghaedi.

Ethics declarations

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

Electronic supplementary material

ESM 1

(DOCX 2735 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Arabi, M., Ghaedi, M. & Ostovan, A. Water compatible molecularly imprinted nanoparticles as a restricted access material for extraction of hippuric acid, a biological indicator of toluene exposure, from human urine. Microchim Acta 184, 879–887 (2017). https://doi.org/10.1007/s00604-016-2063-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-016-2063-5

Keywords

Navigation