Skip to main content
SpringerLink
Log in

Development of novel sol–gel coatings by chemically bonded ionic liquids for stir bar sorptive extraction—application for the determination of NSAIDS in real samples

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

Abstract

In this work, a novel ionic liquid (IL) chemically bonded sol–gel coating was prepared for stir bar sorptive extraction (SBSE) of nonsteroidal anti-inflammatory drugs (NSAIDs) followed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). By using γ-(methacryloxypropyl)trimethoxysilane (KH-570) as a bridging agent, 1-allylimidazolium tetrafluoroborate ([AIM][BF4]) was chemically bonded onto the bare stir bar, and the prepared IL-bonded sol–gel stir bar coating showed higher extraction efficiency and better adsorption/desorption kinetics for target NSAIDs over other polydimethylsiloxane (PDMS)-based or monolithic stir bar coatings. The mechanical strength and durability (chemical/thermal stability) of the prepared IL-bonded sol–gel coating were excellent. The influencing factors of SBSE, such as sample pH, salt effect, stirring rate, extraction time, desorption solvent, and desorption time, were optimized, and the analytical performance of the developed SBSE-HPLC-UV method was evaluated under the optimized conditions. The limits of detection (LODs) of the proposed method for three NSAIDs were in the range of 0.23–0.31 μg L−1, and the enrichment factors (EFs) were in the range of 51.6–56.3 (theoretical enrichment factor was 100). The reproducibility was also investigated at concentrations of 5, 20, and 100 μg L−1, and the relative standard deviations (RSDs) were found to be less than 9.5, 7.5, and 7.6 %, respectively. The proposed method was successfully applied for the determination of NSAIDs in environmental water, urine, and milk samples.

ᅟ

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

Access this article

Log in via an institution

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
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Thun MJ, Henley SJ, Patrono C (2002) Nonsteroidal anti-inflammatory drugs as anticancer agents: mechanistic, pharmacologic, and clinical issues. J Natl Cancer Inst 94:252–266

    Article  CAS  Google Scholar 

  2. Roberts LJ, Morrow JD (2011) Analgesic-antipyretic and anti-inflammatory agents and drugs employed in the treatment of gout. In: Hardman JG, Limbird LE, Gilman AG (eds) Goodman & Gilman’s the pharmacological basis of therapeutics, 10th edn. McGraw-Hill, New York, pp 703–705

    Google Scholar 

  3. Vane JR (1971) Inhibition of prostaglandin synthesis as a mechanism of action for the aspirin-like drugs. Nat New Biol 231:232–235

    Article  CAS  Google Scholar 

  4. Isidori M, Lavorgna M, Nardelli A, Parrella A, Previtera L, Rubino M (2005) Ecotoxicity of naproxen and its phototransformation products. Sci Total Environ 348:93–101

    Article  CAS  Google Scholar 

  5. Kosjek T, Health E, Krbavčič A (2005) Determination of non-steroidal anti-inflammatory drug (NSAIDs) residues in water samples. Environ Int 31:679–685

    Article  CAS  Google Scholar 

  6. Georges H, Jarecki I, Netter P, Magdalou J, Lapicque F (1999) Glycation of human serum albumin by acylglucuronides of nonsteroidal anti-inflammatory drugs of the series of phenylpropionates. Life Sci 65:151–156

    Article  Google Scholar 

  7. Aguilar-Arteaga K, Rodriguez JA, Miranda JM, Medina J, Barrado E (2010) Determination of non-steroidal anti-inflammatory drugs in wastewaters by magnetic matrix solid phase dispersion-HPLC. Talanta 80:1152–1157

    Article  CAS  Google Scholar 

  8. Samaras VG, Thomaidis NS, Stasinakis AS, Lekkas TD (2011) An analytical method for the simultaneous trace determination of acidic pharmaceuticals and phenolic endocrine disrupting chemicals in wastewater and sewage sludge by gas chromatography-mass spectrometry. Anal Bioanal Chem 399:2549–2561

    Article  CAS  Google Scholar 

  9. Macià A, Borrull F, Aguilar C, Calull M (2004) Application of capillary electrophoresis with different sample stacking strategies for the determination of a group of nonsteroidal anti-inflammatory drugs in the low μg·L-1 concentration range. Electrophoresis 25:428–436

  10. Payán MR, López MAB, Torres RF, Navarro MV, Mochón MC (2011) Electromembrane extraction (EME) and HPLC determination of non-steroidal anti-inflammatory drugs (NSAIDs) in wastewater samples. Talanta 85:394–399

    Article  Google Scholar 

  11. Quintana JB, Rodil R, Reemtsma T (2004) Suitability of hollow fiber liquid-phase microextraction for the determination of acidic pharmaceuticals in wastewater by liquid chromatography-electrospray tandem mass spectrometry without matrix effects. J Chromatogr A 1601:19–26

    Article  Google Scholar 

  12. Kot-Wasik A, Debska J, Wasik A, Namieśnik J (2006) Determination of non-steroidal anti-inflammatory drugs in natural waters using off-line and on-line SPE followed by LC coupled with DAD-MS. Chromatographia 64:13–21

    Article  CAS  Google Scholar 

  13. Sun Z, Schüssler W, Sengl M, Niessner R, Knopp D (2008) Selective trace analysis of diclofenac in surface and wastewater samples using solid-phase extraction with a new molecularly imprinted polymer. Anal Chim Acta 620:73–81

    Article  CAS  Google Scholar 

  14. Magnér J, Filipovic M, Alsberg T (2010) Application of a novel solid-phase-extraction sampler and ultra-performance liquid chromatography quadrupole-time-of-flight mass spectrometry for determination of pharmaceutical residues in surface sea water. Chemosphere 80:1255–1260

    Article  Google Scholar 

  15. Ibrahim WAW, Keyon ASA, Prastomo N, Matsuda A (2011) Synthesis and characterization of polydimethylsiloxane-cyanopropyltriethoxysilane-derived hybrid coating for stir bar sorptive extraction. J Sol-gel Sci Technol 59:128–134

    Article  CAS  Google Scholar 

  16. Silva ARM, Portugal FCM, Nogueira JMF (2008) Advances in stir bar sorptive extraction for the determination of acidic pharmaceuticals in environmental water matrices: comparison between polyurethane and polydimethylsiloxane polymeric phases. J Chromatogr A 1209:10–16

    Article  CAS  Google Scholar 

  17. Baltussen E, Sandra P, David F, Cramers C (1999) Stir bar sorptive extraction (SBSE), a novel extraction technique for aqueous samples: theory and principles. J Microcolumn Sep 11:737–747

    Article  CAS  Google Scholar 

  18. Hu C, He M, Chen BB, Hu B (2013) A sol-gel polydimethylsiloxane/polythiophene coated stir bar sorptive extraction combined with gas chromatography-flame photometric detection for the determination of organophosphorus pesticides in environmental water samples. J Chromatogr A 1275:25–31

    Article  CAS  Google Scholar 

  19. Duy SV, Fayad PB, Barbeau B, Prévost M, Sauvé S (2012) Using a novel sol-gel stir bar sorptive extraction method for the analysis of steroid hormones in water by laser diode thermal desorption/atmospheric chemical ionization tandem mass spectrometry. Talanta 101:337–345

    Article  Google Scholar 

  20. Gilart N, Cormack PAG, Marcé RM, Borrull F, Fontanals N (2013) Preparation of a polar monolithic coating for stir bar sorptive extraction of emerging contaminants from wastewaters. J Chromatogr A 1295:42–47

    Article  CAS  Google Scholar 

  21. Huang XJ, Chen LL, Chen M, Yuan DX, Nong SY (2013) Sensitive monitoring of penicillin antibiotics in milk and honey treated by stir bar sorptive extraction based on monolith and LC-electrospray MS detection. J Sep Sci 36:907–915

    Article  CAS  Google Scholar 

  22. Zhan W, Wei FD, Xu GH, Cai Z, Du SH, Zhou XM, Li F, Hu Q (2012) Highly selective stir bar coated with dummy molecularly imprinted polymers for trace analysis of bisphenol A in milk. J Sep Sci 35:1036–1043

    Article  CAS  Google Scholar 

  23. Dupont J, de Souza RF, Suarez PAZ (2002) Ionic liquid (molten salt) phase organometallic catalysis. Chem Rev 102:3667–3691

    Article  CAS  Google Scholar 

  24. Maiti A, Rogers RD (2011) A correlation-based predictor for pair-association in ionic liquids. Phys Chem Phys 13:12138–12145

    Article  CAS  Google Scholar 

  25. Blanchard LA, Hancu D, Beckman EJ, Brennecke JF (1999) Green processing using ionic liquids and CO2. Nature 399:28–29

    Article  Google Scholar 

  26. Cruz-Vera M, Lucena R, Cárdenas S, Valcárcel M (2008) Ionic liquid-based dynamic liquid-phase microextraction: application to the determination of anti-inflammatory drugs in urine samples. J Chromatogr A 1202:1–7

    Article  CAS  Google Scholar 

  27. Shearrow AM, Harris GA, Fang L, Sekhar PK, Nguyen LT, Turner EB, Bhansali S, Malik A (2009) Ionic liquid-mediated sol-gel coatings for capillary microextraction. J Chromatogr A 1216:5449–5458

    Article  CAS  Google Scholar 

  28. Gao Z, Deng YH, Hu XB, Yang SG, Sun C, He H (2013) Determination of organophosphate esters in water samples using an ionic liquid-based sol-gel fiber for headspace solid-phase microextraction coupled to gas chromatography-flame photometric detector. J Chromatogr A 1300:141–150

    Article  CAS  Google Scholar 

  29. Martín-Calero A, Ayala JH, González V, Afonso AM (2009) Ionic liquids as desorption solvents and memory effect suppressors in heterocyclic aromatic amines determination by SPME-HPLC fluorescence. Anal Bioanal Chem 394:937–946

    Article  Google Scholar 

  30. Zhou X, Xie PF, Wang J, Zhang BB, Liu MM, Liu HL, Feng XH (2011) Preparation and characterization of novel crown ether functionalized ionic liquid-based solid-phase microextraction coatings by sol-gel technology. J Chromatogr A 1218:3571–3580

    Article  CAS  Google Scholar 

  31. Sarafraz-Yazdi A, Vatani H (2013) A solid phase microextraction coating based on ionic liquid sol-gel technique for determination of benzene, toluene, ethylbenzene and o-xylene in water samples using gas chromatography flame ionization detector. J Chromatogr A 1300:104–111

    Article  CAS  Google Scholar 

  32. He Y, Pohl J, Engel R, Rothman L, Thomas M (2009) Preparation of ionic liquid based solid-phase microextraction fiber and its application to forensic determination of methamphetamine and amphetamine in human urine. J Chromatogr A 1216:4824–4830

    Article  CAS  Google Scholar 

  33. Liu JF, Li N, Jiang GB, Li JM, Jönsson JA, Wen MJ (2005) Disposable ionic liquid coating for headspace solid-phase microextraction of benzene, toluene, ethylbenzene, and xylenes in paints followed by gas chromatography-flame ionization detection. J Chromatogr A 1066:27–32

    Article  CAS  Google Scholar 

  34. Amini R, Rouhollahi A, Adibi M, Mehdinia A (2011) A novel reusable ionic liquid chemically bonded fused-silica fiber for headspace solid-phase microextraction/gas chromatography-flame ionization detection of methyl tert-butyl ether in a gasoline sample. J Chromatogr A 1218:130–136

    Article  CAS  Google Scholar 

  35. Wanigasekara E, Perera S, Crank JA, Sidisky L, Shirey R, Berthod A, Armstrong DW (2010) Bonded ionic liquid polymeric material for solid-phase microextraction GC analysis. Anal Bioanal Chem 396:511–524

    Article  CAS  Google Scholar 

  36. Liu MM, Zhou X, Chen YY, Liu HL, Feng XH, Qiu GH, Liu F, Zeng ZR (2010) Innovative chemically bonded ionic liquids-based sol-gel coatings as highly porous, stable and selective stationary phases for solid phase microextraction. Anal Chim Acta 683:96–106

    Article  CAS  Google Scholar 

  37. Zhou X, Shang J, Liu MM, Liu HL, Hao R, Feng XH, Liu F (2010) Preparation of novel ionic liquids-based sol-gel coatings for solid-phase microextraction. Acta Chim Sinica 68:1749–1757

    CAS  Google Scholar 

  38. Zhou X, Shao X, Shu JJ, Liu MM, Liu HL, Feng XH, Liu F (2012) Thermally stable ionic liquid-based sol-gel coating for ultrasonic extraction solid-phase microextraction-gas chromatography determination of phthalate esters in agricultural plastic films. Talanta 89:129–135

    Article  CAS  Google Scholar 

  39. López-Darias J, Pino V, Anderson JL, Graham CM, Afonso AM (2010) Determination of water pollutants by direct-immersion solid-phase microextraction using polymeric ionic liquid coatings. J Chromatogr A 1217:1236–1243

    Article  Google Scholar 

  40. López-Darias J, Pino V, Meng YJ, Anderson JL, Afonso AM (2010) Utilization of a benzyl functionalized polymeric ionic liquid for the sensitive determination of polycyclic aromatic hydrocarbons, parabens and alkylphenols in waters using solid-phase microextraction coupled to gas chromatography-flame ionization detection. J Chromatogr A 1217:7189–7197

    Article  Google Scholar 

  41. Meng YJ, Pino V, Anderson JL (2011) Role of counteranions in polymeric ionic liquid-based solid-phase microextraction coatings for the selective extraction of polar compounds. Anal Chim Acta 687:141–149

    Article  CAS  Google Scholar 

  42. Meng YJ, Anderson JL (2010) Tuning the selectivity of polymeric ionic liquid sorbent coatings for the extraction of polycyclic aromatic hydrocarbons using solid-phase microextraction. J Chromatogr A 1217:6143–6152

    Article  CAS  Google Scholar 

  43. Yu CH, Yao ZM, Hu B (2009) Preparation of polydimethylsiloxane/beta-cyclodextrin/divinylbenzene coated “dumbbell-shaped” stir bar and its application to the analysis of polycyclic aromatic hydrocarbons and polycyclic aromatic sulfur heterocycles compounds in lake water and soil by high performance liquid chromatography. Anal Chim Acta 641:75–82

    Article  CAS  Google Scholar 

  44. Yu CH, Hu B (2012) C18-coated stir bar sorptive extraction combined with high performance liquid chromatography-electrospray tandem mass spectrometry for the analysis of sulfonamides in milk and milk powder. Talanta 90:77–84

    Article  CAS  Google Scholar 

  45. Sousa MA, Goncalves C, Cunha E, Hajšlová J, Alpendurada MF (2011) Cleanup strategies and advantages in the determination of several therapeutic classes of pharmaceuticals in wastewater samples by SPE-LC-MS/MS. Anal Bioanal Chem 399:807–822

    Article  CAS  Google Scholar 

  46. Hoshina K, Horiyama S, Matsunaga H, Haginaka J (2011) Simultaneous determination of non-steroidal anti-inflammatory drugs in river water samples by liquid chromatography-tandem mass spectrometry using molecularly imprinted polymers as a pretreatment column. J Pharmaceut Biomed 55:916–922

    Article  CAS  Google Scholar 

  47. Luo YB, Zheng HB, Wang JX, Gao Q, Yu QW, Feng YQ (2011) An anionic exchange stir rod sorptive extraction based on monolithic material for the extraction of non-steroidal anti-inflammatory drugs in environmental aqueous samples. Talanta 86:103–108

    Article  CAS  Google Scholar 

  48. Fan Y, Feng YQ, Da SL, Wang ZH (2005) In-tube solid phase microextraction using a beta-cyclodextrin coated capillary coupled to high performance liquid chromatography for determination of non-steroidal anti-inflammatory drugs in urine samples. Talanta 65:111–117

    CAS  Google Scholar 

Download references

Acknowledgments

Financial supports from the National Nature Science Foundation of China (20775057), the Science Fund for Creative Research Groups of NSFC (Nos. 20621502 and 20921062) and the State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, and Chinese Academy of Sciences (No. KF2010-04) are gratefully acknowledged.

Author information

Authors and Affiliations

  1. Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan, 430072, China

    Wenying Fan, Xiangju Mao, Man He, Beibei Chen & Bin Hu

Authors
  1. Wenying Fan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiangju Mao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Man He
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Beibei Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bin Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Bin Hu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Fig S1

(PDF 2.98 MB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Fan, W., Mao, X., He, M. et al. Development of novel sol–gel coatings by chemically bonded ionic liquids for stir bar sorptive extraction—application for the determination of NSAIDS in real samples. Anal Bioanal Chem 406, 7261–7273 (2014). https://doi.org/10.1007/s00216-014-8141-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-014-8141-9

Keywords

Search

Navigation