Skip to main content
SpringerLink
Log in

Nanoporous Polyimide Microspheres Solid Phase Extraction Coupled to Liquid Chromatography with Fluorescence Detection to Determine Fluoroquinolones in Water and Food Samples

  • Original
  • Published:
Chromatographia Aims and scope Submit manuscript

Abstract

In this work, nanoporous polyimide (PI) microspheres (NPMs) were prepared in bulk using the spray phase inversion technique. Due to the right size and shape, open nanopores with diameters of 10–70 nm, a large surface area of 52 m2 g−1, and abundant chemical extraction property, these NPMs were successfully used as solid phase extraction (SPE) sorbents. Combined with an ultra-performance liquid chromatography-fluorescence detector (NPM-SPE-UPLC-FLD), five fluoroquinolones (FQs) were quantified successfully in environmental water and food samples. After the NPMs with 50–75 μm diameters were collected by sieving, packed into an SPE cartridge, and conditioned by rinsing with acetonitrile and water, FQs in water samples were extracted and eluted with high recoveries between 75.5% and 112.3%. A breakthrough volume of 380 mL was obtained with only 20 mg of NPM sorbents. Under optimal conditions, the limits of detection for FQs in spiked purified water were 0.002–0.011 μg L−1, and the linear range was more than three orders of magnitude (0.004–10 μg L−1) with good correlation coefficients of 0.9984–0.9996. The intra-batch relative standard deviations (RSDs) of the NPMs were 0.5%–9.8%, and the inter-batch RSDs were 1.6%–13.4%. Finally, the NPM-SPE-UPLC-FLD method was successfully applied to water, egg and milk samples. These results demonstrated that NPMs are promising candidates for SPE sorbents due to their convenient preparation and excellent performance in environmental water and food samples.

Graphical abstract

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. Poole CF (2016) Encyclopedia of analytical science: EXTRACTION | solid-phase extraction, 3rd edn. Elsevier, UK, pp 89–99

    Google Scholar 

  2. Needham L, Paschal D, Rollen ZJ, Liddle J, Bayse D (1979) Determination of paraquat in marijuana by reversed-phase paired-ion high performance liquid chromatography. J Chromatogr Sci 17:87–90. https://doi.org/10.1093/chromsci/17.2.87

    Article  CAS  PubMed  Google Scholar 

  3. Desilets CP, Rounds MA, Regnier FE (1991) Semipermeable-surface reversed-phase media for high performance liquid chromatography. J Chromatogr A 544:25–39. https://doi.org/10.1016/S0021-9673(01)83976-5

    Article  CAS  Google Scholar 

  4. Dias NC, Poole CF (2002) Mechanistic study of the sorption properties of OASIS® HLB and its use in solid-phase extraction. Chromatographia 56:269–275. https://doi.org/10.1007/BF02491931

    Article  CAS  Google Scholar 

  5. Dias JV, Cutillas V, Lozano A, Pizzutti IR, Fernández-Alba AR (2016) Determination of pesticides in edible oils by liquid chromatography-tandem mass spectrometry employing new generation materials for dispersive solid phase extraction clean-up. J Chromatogr A 1462:8–18. https://doi.org/10.1016/j.chroma.2016.07.072

    Article  CAS  PubMed  Google Scholar 

  6. Ding TH, Lin HH, Whang CW (2005) Determination of chromium (III) in water by solid-phase microextraction with a polyimide-coated fiber and gas chromatography-flame photometric detection. J Chromatogr A 1062:49–55. https://doi.org/10.1016/j.chroma.2004.11.034

    Article  CAS  PubMed  Google Scholar 

  7. Ma XY, Yan XH, Wu Y, Qiu QK, Li YS, Wu DP, Gao P (2021) Freestanding fully porous polyimide membrane for thin film microextraction. Chromatographia 84:549–557. https://doi.org/10.1007/s10337-021-04031-0

    Article  CAS  Google Scholar 

  8. Yan XH, Zhan YY, Zhong DD, Li YS, Wu DP (2018) Electrospun nanofiber cloud for ultrafast solid phase micro-extraction of trace organics in water samples. J Chromatogr A 1574:42–49. https://doi.org/10.1016/j.chroma.2018.09.007

    Article  CAS  PubMed  Google Scholar 

  9. Yan XH, Zhong DD, Zhan YY, Li YS, Wu DP (2019) Porous polyimide particle-coated adsorptive microextraction bar combined with thermal desorption-gas chromatography for rapid determination of parabens in condiments. J Chromatogr A 1601:71–78. https://doi.org/10.1016/j.chroma.2019.05.017

    Article  CAS  PubMed  Google Scholar 

  10. Redgrave LS, Sutton SB, Webber MA, Piddock LJV (2014) Fluoroquinolone resistance: mechanisms, impact on bacteria, and role in evolutionary success. Trends Microbiol 22:438–445. https://doi.org/10.1016/j.tim.2014.04.007

    Article  CAS  PubMed  Google Scholar 

  11. Gbylik-Sikorska M, Posyniak A, Sniegocki T, Zmudzki J (2015) Liquid chromatography-tandem mass spectrometry multiclass method for the determination of antibiotics residues in water samples from water supply systems in food-producing animal farms. Chemosphere 119:8–15. https://doi.org/10.1016/j.chemosphere.2014.04.105

    Article  CAS  PubMed  Google Scholar 

  12. Speltini A, Sturini M, Maraschi F, Consoli L, Zeffiro A, Profumo A (2015) Graphene-derivatized silica as an efficient solid-phase extraction sorbent for pre-concentration of fluoroquinolones from water followed by liquid-chromatography fluorescence detection. J Chromatogr A 1379:9–15. https://doi.org/10.1016/j.chroma.2014.12.047

    Article  CAS  PubMed  Google Scholar 

  13. Chen B, Wang WD, Huang YM (2012) Cigarette filters as adsorbents of solid-phase extraction for determination of fluoroquinolone antibiotics in environmental water samples coupled with high-performance liquid chromatography. Talanta 88:237–243. https://doi.org/10.1016/j.talanta.2011.09.066

    Article  CAS  PubMed  Google Scholar 

  14. Zheng H, Mo J, Zhang Y, Gao Q, Ding J, Yu Q, Feng Y (2014) Facile synthesis of magnetic molecularly imprinted polymers and its application in magnetic solid phase extraction for fluoroquinolones in milk samples. J Chromatogr A 1329:17–23. https://doi.org/10.1016/j.chroma.2013.12.083

    Article  CAS  PubMed  Google Scholar 

  15. Herrera-Herrera AV, Hernández-Borges J, Rodríguez-Delgado MÁ (2009) Fluoroquinolone antibiotic determination in bovine, ovine and caprine milk using solid-phase extraction and high-performance liquid chromatography-fluorescence detection with ionic liquids as mobile phase additives. J Chromatogr A 1216:7281–7287. https://doi.org/10.1016/j.chroma.2009.02.025

    Article  CAS  PubMed  Google Scholar 

  16. Pang JL, Liao YM, Huang XJ, Ye ZW, Yuan DX (2019) Metal-organic framework-monolith composite-based in-tube solid phase microextraction on-line coupled to high-performance liquid chromatography-fluorescence detection for the highly sensitive monitoring of fluoroquinolones in water and food samples. Talanta 199:499–506. https://doi.org/10.1016/j.talanta.2019.03.019

    Article  CAS  PubMed  Google Scholar 

  17. Hong JW, Liu XM, Yang XY, Wang YS, Zhao LS (2021) Ionic liquid-based dispersive liquid-liquid microextraction followed by magnetic solid-phase extraction for determination of quinolones. Mikrochim Acta 189:8. https://doi.org/10.1007/s00604-021-05077-5

    Article  CAS  PubMed  Google Scholar 

  18. Wang R, Li S, Chen DW, Zhao YF, Wu YN, Qi KM (2021) Selective extraction and enhanced-sensitivity detection of fluoroquinolones in swine body fluids by liquid chromatography-high resolution mass spectrometry: application in long-term monitoring in livestock. Food Chem. https://doi.org/10.1016/j.foodchem.2020.128269

    Article  PubMed  PubMed Central  Google Scholar 

  19. Vakh C, Pochivalov A, Koronkiewicz S, Kalinowski S, Postnov V, Bulatov A (2019) A chemiluminescence method for screening of fluoroquinolones in milk samples based on a multi-pumping flow system. Food Chem 270:10–16. https://doi.org/10.1016/j.foodchem.2018.07.073

    Article  CAS  PubMed  Google Scholar 

  20. Springer VH, Lista AG (2015) In-line coupled single drop liquid-liquid-liquid microextraction with capillary electrophoresis for determining fluoroquinolones in water samples. Electrophoresis 36:1572–1579. https://doi.org/10.1002/elps.201400602

    Article  CAS  PubMed  Google Scholar 

  21. Shen K, Zou X, Wang J (2022) Simultaneous determination of the four key fluoroquinolones and two antipsychotics in fish and shrimp by LC-MS/MS. Food Addit Contam Part A Chem Anal Control Expo Risk Assess 39:678–686. https://doi.org/10.1080/19440049.2022.2032381

    Article  CAS  PubMed  Google Scholar 

  22. Ašperger D, Tišler V, Zrnčić M, Mutavdžić Pavlović D, Babić S, Horvat AJM, Kaštelan-Macan M (2014) HPLC–DAD–FLD determination of veterinary pharmaceuticals in pharmaceutical industry wastewater with precolumn derivatization using fluorescamine. Chromatographia 77:1059–1066. https://doi.org/10.1007/s10337-014-2685-x

    Article  CAS  Google Scholar 

  23. Ribeiro CC, Orlando RM, Rohwedder JJR, Reyes FGR, Rath S (2016) Electric field-assisted solid phase extraction and cleanup of ionic compounds in complex food matrices: fluoroquinolones in eggs. Talanta 152:498–503. https://doi.org/10.1016/j.talanta.2016.02.047

    Article  CAS  PubMed  Google Scholar 

  24. He K, Blaney L (2015) Systematic optimization of an SPE with HPLC-FLD method for fluoroquinolone detection in waste water. J Hazard Mater 282:96–105. https://doi.org/10.1016/j.jhazmat.2014.08.027

    Article  CAS  PubMed  Google Scholar 

  25. Speltini A, Maraschi F, Govoni R, Milanese C, Profumo A, Malavasi L, Sturini M (2017) Facile and fast preparation of low-cost silica-supported graphitic carbon nitride for solid-phase extraction of fluoroquinolone drugs from environmental waters. J Chromatogr A 1489:9–17. https://doi.org/10.1016/j.chroma.2017.02.002

    Article  CAS  PubMed  Google Scholar 

  26. Wang R, Yuan Y, Yang X, Han Y, Yan H (2015) Polymethacrylate microparticles covalently functionalized with an ionic liquid for solid-phase extraction of fluoroquinolone antibiotics. Microchim Acta 182:2201–2208. https://doi.org/10.1007/s00604-015-1544-2

    Article  CAS  Google Scholar 

  27. Wang GN, Yang K, Liu HZ, Feng MX, Wang JP (2016) Molecularly imprinted polymer-based solid phase extraction combined high performance liquid chromatography for determination of fluoroquinolones in milk. Anal Methods 8:5511–5518. https://doi.org/10.1039/c6ay00810k

    Article  CAS  Google Scholar 

  28. Benito-Peña E, Urraca JL, Sellergren B, Moreno-Bondi MC (2008) Solid-phase extraction of fluoroquinolones from aqueous samples using a water-compatible stochiometrically imprinted polymer. J Chromatogr A 1208:62–70. https://doi.org/10.1016/j.chroma.2008.08.109

    Article  CAS  PubMed  Google Scholar 

  29. He X, Wang GN, Yang K, Liu HZ, Wu XJ, Wang JP (2017) Magnetic graphene dispersive solid phase extraction combining high performance liquid chromatography for determination of fluoroquinolones in foods. Food Chem 221:1226–1231. https://doi.org/10.1016/j.foodchem.2016.11.035

    Article  CAS  PubMed  Google Scholar 

  30. Wang X, Zhao L, Sun Z, Gong B (2019) Preparation of ofloxacin-restricted access media–molecularly imprinted polymers for its selective recognition of ofloxacin in milk samples. Chromatographia 82:1041–1050. https://doi.org/10.1007/s10337-019-03738-5

    Article  CAS  Google Scholar 

  31. Qiu QK, Wu Y, Yan XH, Li YS, Li JL, Chen YB, Wu DP (2021) Porous electrospun microfibers for low flow-resistant solid phase extraction of fluoroquinolones in tap water, egg and milk samples. J Chromatogr A 1661:462719. https://doi.org/10.1016/j.chroma.2021.462719

    Article  CAS  PubMed  Google Scholar 

Download references

Funding

This work was supported by the Natural Science Foundation of Zhejiang (LGG20B050001, 2019R02009, 2022C01029), Natural Science Foundation of Anhui (202003c08020001), Natural Science Foundation of Ningbo (2020Z036) and the K.C. Wong Magna Fund of Ningbo University.

Author information

Authors and Affiliations

  1. State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-Products, State Key Laboratory Base of Novel Functional Materials and Preparation Science, School of Materials Science and Chemical Engineering, Ningbo University, Ningbo, 315211, Zhejiang, China

    Yi Wu, Dongdong Zhong, Qiankun Qiu, Xiaohui Yan & Dapeng Wu

  2. Zhejiang Hymater New Materials Co., Ltd, Zhejiang, 315200, China

    Dapeng Wu

Authors
  1. Yi Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dongdong Zhong
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qiankun Qiu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiaohui Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Dapeng Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Dapeng Wu.

Ethics declarations

Conflict of interest

There are no conflicts of interest.

Ethical approval

This article does not contain any studies with animals or human participants.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

10337_2022_4196_MOESM1_ESM.docx

Supplementary file1 Supplementary data associated with this article (Fig. S1-S6, Table S1-S3) can be found in the online version (DOCX 1071 KB)

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wu, Y., Zhong, D., Qiu, Q. et al. Nanoporous Polyimide Microspheres Solid Phase Extraction Coupled to Liquid Chromatography with Fluorescence Detection to Determine Fluoroquinolones in Water and Food Samples. Chromatographia 85, 939–948 (2022). https://doi.org/10.1007/s10337-022-04196-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-022-04196-2

Keywords

Search

Navigation