Microchimica Acta

, 186:759 | Cite as

Hybrid monoliths with metal-organic frameworks in spin columns for extraction of non-steroidal drugs prior to their quantitation by reversed-phase HPLC

  • Myrthe Giesbers
  • Enrique Javier Carrasco-CorreaEmail author
  • Ernesto F. Simó-Alfonso
  • José Manuel Herrero-MartínezEmail author
Original Paper


A (glycidyl methacrylate)-co-(ethylene glycol dimethacrylate) polymer (poly(GMA-co-EDMA)) was functionalized with metal-organic frameworks (MOF) and used as a sorbent for solid-phase extraction (SPE). The polymeric sorbent was prepared in-situ by photopolymerization in a previously wall-modified spin column, and then modified with an amino-modified MOF of type NH2-MIL-101(Cr). The sorbents were used for the extraction of nonsteroidal anti-inflammatory drugs (NSAIDs) from human urine samples. The sorbent was compared with the parent monolith and embedded approach, where the MOF particles are admixed in the polymerization mixture before the in-situ polymerization in the modified spin column. SPE is performed by percolating the sample solutions in a centrifuge, which streamlines the SPE steps. The hybrid composites were characterized by scanning electron microscopy and nitrogen intrusion porosimetry. Three NSAIDs (ketoprofen, flurbiprofen, and ibuprofen) were tested. They were eluted from the sorbent with acidified water-acetonitrile mixtures and subsequently analyzed by reversed-phase HPLC with UV detection. The detection limits varied in the range from 0.1 to 7 μg·L−1, and the precisions (relative standard deviation) were <14% in all the cases. The recoveries were between 71.0 and 78.0% in spiked urine samples.

Graphical abstract

A hybrid monolith modified with amino-modified MOF [named NH2-MIL-101(Cr)] in wall-modified spin columns was prepared. The resulting micro-extraction device was applied to the extraction and preconcentration of non-steroidal anti-inflammatory drugs.


Sample preparation Solid-phase (micro)extraction Polymer organic monoliths Surface modification Embedded approach In-situ polymerization Microporous crystalline materials Centrifuge extraction procedure Polypropylene wall modification Photografting 



Financial support from PROMETEO/2016/145 (Conselleria de Educación, Investigación, Cultura y Deporte, Generalitat Valenciana, Spain) and RTI2018-095536-B-I00 (Ministry of Science, Innovation and Universities, Spain) is gratefully acknowledged. E. J. C.-C. thanks the Generalitat Valenciana for a VALi+D postdoctoral research contract.

Compliance with ethical standards

Conflict of interest

The authors have declared no conflict of interest.

Supplementary material

604_2019_3923_MOESM1_ESM.docx (558 kb)
ESM 1 (DOCX 558 kb)


  1. 1.
    Carrasco-Correa EJ, Martínez-Vilata A, Herrero-Martínez JM, Parra JB, Maya F, Cerdà V, Palomino Cabello C, Turnes Palomino G, Svec F (2016) Incorporation of zeolitic imidazolate framework (ZIF-8)-derived nanoporous carbons in methacrylate polymeric monoliths for capillary electrochromatography. Talanta 164:348–354. CrossRefPubMedGoogle Scholar
  2. 2.
    Zhang X, Liang Q, Han Q, Wan W, Ding M (2016) Metal–organic frameworks@graphene hybrid aerogels for solid-phase extraction of nonsteroidal anti-inflammatory drugs and selective enrichment of proteins. Analyst 141:4219–4226. CrossRefGoogle Scholar
  3. 3.
    Maya F, Palomino Cabello C, Figuerola A, Turnes Palomino G, Cerdà V (2018) Immobilization of metal–organic frameworks on supports for sample preparation and chromatographic separation. Chromatographia 82(1):361–375. CrossRefGoogle Scholar
  4. 4.
    Gu ZY, Yang CX, Chang N, Yan XP (2012) Metal–organic frameworks for analytical chemistry: from sample collection to chromatographic separation. Acc Chem Res 45(5):734–745. CrossRefPubMedGoogle Scholar
  5. 5.
    Lv Y, Tan X, Svec F (2016) Preparation and applications of monolithic structures containing metal-organic frameworks. J Sep Sci 40(1):272–287. CrossRefPubMedGoogle Scholar
  6. 6.
    Yu LQ, Wang LY, Su FH, Hao PY, Wang H, Lv YK (2018) A gate-opening controlled metal-organic framework for selective solid-phase microextraction of aldehydes from exhaled breath of lung cancer patients. Microchim Acta 185(6):307. CrossRefGoogle Scholar
  7. 7.
    Tan SC, Lee HK (2019) A metal-organic framework of type MIL-101(Cr) for emulsification-assisted micro-solid-phase extraction prior to UHPLC-MS/MS analysis of polar estrogens. Microchim Acta 186(3):165. CrossRefGoogle Scholar
  8. 8.
    Li W, Chen N, Zhu Y, Shou D, Zhi M, Zeng X (2019) A nanocomposite consisting of an amorphous seed and a molecularly imprinted covalent organic framework shell for extraction and HPLC determination of nonsteroidal anti-inflammatory drugs. Microchim Acta 186(2):76. CrossRefGoogle Scholar
  9. 9.
    Chen Z, Yu C, Xi J, Tang S, Bao T, Zhang J (2019) A hybrid material prepared by controlled growth of a covalent organic framework on amino-modified MIL-68 for pipette tip solid-phase extraction of sulfonamides prior to their determination by HPLC. Microchim Acta 186(6):393. CrossRefGoogle Scholar
  10. 10.
    Mirzajani R, Kardani F, Ramezani Z (2019) A nanocomposite consisting of graphene oxide, zeolite imidazolate framework 8, and a molecularly imprinted polymer for (multiple) fiber solid phase microextraction of sterol and steroid hormones prior to their quantitation by HPLC. Microchim Acta 186(3):129. CrossRefGoogle Scholar
  11. 11.
    Deng ZH, Xu GJ, Wang XL, Wang X, Wang ML, Lin JM, Zhao RS (2018) A Zr(IV)-based porphyrinic metal-organic framework as a solid-phase sorbent for extraction of sulfonamides prior to their quantitation by LC-MS. Microchim Acta 185(10):450. CrossRefGoogle Scholar
  12. 12.
    Yang XQ, Yang CX, Yan XP (2013) Zeolite imidazolate framework-8 as sorbent for on-line solid-phase extraction coupled with high-performance liquid chromatography for the determination of tetracyclines in water and milk samples. J Chromatogr A 1304:28–33. CrossRefPubMedGoogle Scholar
  13. 13.
    Van de Voorde B, Bueken B, Denayer J, De Vos D (2014) Adsorptive separation on metal–organic frameworks in the liquid phase. Chem Soc Rev 43(16):5766–5788. CrossRefPubMedGoogle Scholar
  14. 14.
    Ma W, Li X, Bai Y, Liu H (2018) Applications of metal-organic frameworks as advanced sorbents in biomacromolecules sample preparation. TrAC Trends Anal Chem 109:154–162. CrossRefGoogle Scholar
  15. 15.
    Li D, Bie Z (2017) Metal–organic framework incorporated monolithic capillary for selective enrichment of phosphopeptides. RSC Adv 7(26):15894–15902. CrossRefGoogle Scholar
  16. 16.
    Lyu DY, Yang CX, Yan XP (2015) Fabrication of aluminum terephthalate metal-organic framework incorporated polymer monolith for the microextraction of non-steroidal anti-inflammatory drugs in water and urine samples. J Chromatogr A 1393:1–7. CrossRefPubMedGoogle Scholar
  17. 17.
    Lirio S, Liu WL, Lin CL, Lin CH, Huang HY (2016) Aluminum based metal-organic framework-polymer monolith in solid-phase microextraction of penicillins in river water and milk samples. J Chromatogr A 1428:236–245. CrossRefPubMedGoogle Scholar
  18. 18.
    Shih YH, Wang KY, Singco B, Lin CH, Huang HY (2016) Metal–organic framework–polymer composite as a highly efficient sorbent for sulfonamide adsorption and desorption: effect of Coordinatively unsaturated metal site and topology. Langmuir 32(44):11465–11473. CrossRefPubMedGoogle Scholar
  19. 19.
    Wang H, Li Z, Feng W, Jia Q (2017) Polymer monolith containing an embedded covalent organic framework for the effective enrichment of benzophenones. New J Chem 41(21):13043–13050. CrossRefGoogle Scholar
  20. 20.
    Li X, Wang X, Ma W, Ai W, Bai Y, Ding L, Liu H (2017) Fast analysis of glycosides based on HKUST-1-coated monolith solid-phase microextraction and direct analysis in real-time mass spectrometry. J Sep Sci 40(7):1589–1596. CrossRefPubMedGoogle Scholar
  21. 21.
    Yang JH, Cui CX, Qu LB, Chen J, Zhou XM, Zhang YP (2018) Preparation of a monolithic magnetic stir bar for the determination of sulfonylurea herbicides coupled with HPLC. Microchem J 141:369–376. CrossRefGoogle Scholar
  22. 22.
    Fresco-Cala B, Cárdenas S, Herrero-Martínez JM (2017) Preparation of porous methacrylate monoliths with oxidized single-walled carbon nanohorns for the extraction of nonsteroidal anti-inflammatory drugs from urine samples. Microchim Acta 184(6):1863–1871. CrossRefGoogle Scholar
  23. 23.
    Prakash V, Rodriguez RD, Al-Hamry A, Lipovka A, Dorozhko E, Selyshchev O, Ma B, Sharma S, Mehta SK, Dzhagan V, Mukherjee A, Zahn DRT, Kanounc O, Sheremet E (2019) Flexible plasmonic graphene oxide/heterostructures for dual-channel detection. Analyst 144:3297–3306. CrossRefPubMedGoogle Scholar
  24. 24.
    Yang S, Ye F, Zhang C, Shen S, Zhao S (2015) In situ synthesis of metal–organic frameworks in a porous polymer monolith as the stationary phase for capillary liquid chromatography. Analyst 140(8):2755–2761. CrossRefPubMedGoogle Scholar
  25. 25.
    Serra-Crespo P, Ramos-Fernandez EV, Gascon J, Kapteijn F (2011) Synthesis and characterization of an amino functionalized MIL-101(Al): separation and catalytic properties. Chem Mater 23(10):2565–2572. CrossRefGoogle Scholar
  26. 26.
    Pérez-Cejuela HM, Carrasco-Correa EJ, Shahat A, Simó-Alfonso EF, Herrero-Martínez JM (2018) Incorporation of metal-organic framework amino-modified MIL-101 into glycidyl methacrylate monoliths for nano LC separation. J Sep Sci 42(4):834–842. CrossRefGoogle Scholar
  27. 27.
    Hassan HMA, Beitha MA, Mohamed SK (2017) Salen- Zr(IV) complex grafted into amine-tagged MIL-101(Cr) as a robust multifunctional catalyst for biodiesel production and organic transformation reactions. Appl Surf Sci 412:394–404. CrossRefGoogle Scholar
  28. 28.
    Couck S, Denayer JFM, Baron GV, Rémy T, Gascon J, Kapteijn F (2009) An amine-functionalized MIL-53 metal−organic framework with large separation power for CO2 and CH4. J Am Chem Soc 131(18):6326–6327. CrossRefPubMedGoogle Scholar
  29. 29.
    Weller A, Carrasco-Correa EJ, Belenguer-Sapiña C, De Los Reyes Mauri-Aucejo A, Amorós P, Herrero-Martínez JM (2017) Organo-silica hybrid capillary monolithic column with mesoporous silica particles for separation of small aromatic molecules. Microchim Acta 184(10):3799–3808. CrossRefGoogle Scholar
  30. 30.
    Carrasco-Correa EJ, Ramis-Ramos G, Herrero-Martínez JM (2015) Hybrid methacrylate monolithic columns containing magnetic nanoparticles for capillary electrochromatography. J Chromatogr A 1385:77–84. CrossRefPubMedGoogle Scholar
  31. 31.
    Li Y, Huang C, Yang J, Peng J, Jin J, Ma H, Chen J (2017) Multifunctionalized mesoporous silica as an efficient reversed-phase/anion exchange mixed-mode sorbent for solid-phase extraction of four acidic nonsteroidal anti-inflammatory drugs in environmental water samples. J Chromatogr A 1527:10–17. CrossRefPubMedGoogle Scholar
  32. 32.
    Hu C, He M, Chen B, Hu B (2015) Simultaneous determination of polar and apolar compounds in environmental samples by a polyaniline/hydroxyl multi-walled carbon nanotubes composite-coated stir bar sorptive extraction coupled with high performance liquid chromatography. J Chromatogr A 1394:36–45. CrossRefPubMedGoogle Scholar
  33. 33.
    Jian N, Qian L, Wang C, Li R, Xu Q, Li J (2019) Novel nanofibers mat as an efficient, fast and reusable adsorbent for solid phase extraction of non-steroidal anti-inflammatory drugs in environmental water. J Hazard Mater 363:81–89. CrossRefPubMedGoogle Scholar
  34. 34.
    Amiri A, Mirzaei M, Derakhshanrad S (2019) A nanohybrid composed of polyoxotungstate and graphene oxide for dispersive micro solid-phase extraction of non-steroidal anti-inflammatory drugs prior to their quantitation by HPLC. Microchim Acta 186(8):534. CrossRefGoogle Scholar
  35. 35.
    Ali I, Kulsum U, Al-Othman ZA, Saleem K (2016) Analyses of nonsteroidal anti-inflammatory drugs in human plasma using dispersive nano solid-phase extraction and high-performance liquid chromatography. Chromatographia 79(3–4):145–157. CrossRefGoogle Scholar
  36. 36.
    Luo ZY, Li ZY, Liu HY, Tang MQ, Shi ZG (2015) Click chemistry-based synthesis of water-dispersible hydrophobic magnetic nanoparticles for use in solid phase extraction of non-steroidal anti-inflammatory drugs. Microchim Acta 182(15–16):2585–2591. CrossRefGoogle Scholar
  37. 37.
    Ferrone V, Carlucci M, Ettorre V, Cotellese R, Palumbo P, Fontana A, Siani G, Carlucci G (2018) Dispersive magnetic solid phase extraction exploiting magnetic graphene nanocomposite coupled with UHPLC-PDA for simultaneous determination of NSAIDs in human plasma and urine. J Pharm Biomed Anal 161:280–288. CrossRefPubMedGoogle Scholar
  38. 38.
    Alinezhad H, Amiri A, Tarahomi M, Maleki B (2018) Magnetic solid-phase extraction of non-steroidal anti-inflammatory drugs from environmental water samples using polyamidoamine dendrimer functionalized with magnetite nanoparticles as a sorbent. Talanta 183:149–157. CrossRefPubMedGoogle Scholar
  39. 39.
    Liu S, Li S, Yang W, Gu F, Xu H, Wang T, Sun D, Hou X (2019) Magnetic nanoparticle of metal-organic framework with core-shell structure as and adsorbent for magnetic solid phase extraction of non-steroidal anti-inflammatory drugs. Talanta 194:514–521. CrossRefPubMedGoogle Scholar
  40. 40.
    Baile P, Vidal L, Canals A (2019) A modified zeolite/iron oxide composite as a sorbent for magnetic dispersive solid-phase extraction for the preconcentration of nonsteroidal anti-inflammatory drugs in water and urine samples. J Chromatogr A 1603:33–43. CrossRefPubMedGoogle Scholar
  41. 41.
    Wang T, Liu S, Gao G, Zhao PD (2017) Magnetic solid phase extraction of non-steroidal anti-inflammatory drugs from water samples using a metal organic framework of type Fe3O4/MIL-101(Cr), and their quantitation by UPLC-MS/MS. Microchim Acta 184(8):1–10. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  • Myrthe Giesbers
    • 1
  • Enrique Javier Carrasco-Correa
    • 1
    Email author
  • Ernesto F. Simó-Alfonso
    • 1
  • José Manuel Herrero-Martínez
    • 1
    Email author
  1. 1.Department of Analytical Chemistry, Faculty of ChemistryUniversity of ValenciaBurjassotSpain

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