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.
This is a preview of subscription content, log in to check access.
Buy single article
Instant unlimited access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
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. https://doi.org/10.1016/j.talanta.2016.11.027
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. https://doi.org/10.1039/c6an00353b
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. https://doi.org/10.1007/s10337-018-3616-z
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. https://doi.org/10.1021/ar2002599
Lv Y, Tan X, Svec F (2016) Preparation and applications of monolithic structures containing metal-organic frameworks. J Sep Sci 40(1):272–287. https://doi.org/10.1002/jssc.201600423
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. https://doi.org/10.1007/s00604-017-2843-1
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. https://doi.org/10.1007/s00604-019-3289-9
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. https://doi.org/10.1007/s00604-018-3187-6
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. https://doi.org/10.1007/s00604-019-3513-7
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. https://doi.org/10.1007/s00604-018-3217-4
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. https://doi.org/10.1007/s00604-018-2985-1
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. https://doi.org/10.1016/j.chroma.2013.06.064
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. https://doi.org/10.1039/C4CS00006D
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. https://doi.org/10.1016/j.trac.2018.10.003
Li D, Bie Z (2017) Metal–organic framework incorporated monolithic capillary for selective enrichment of phosphopeptides. RSC Adv 7(26):15894–15902. https://doi.org/10.1039/C7RA00263G
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. https://doi.org/10.1016/j.chroma.2015.03.020
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. https://doi.org/10.1016/j.chroma.2015.05.043
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. https://doi.org/10.1021/acs.langmuir.6b03067
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. https://doi.org/10.1039/C7NJ02512B
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. https://doi.org/10.1002/jssc.201601115
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. https://doi.org/10.1016/j.microc.2018.05.049
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. https://doi.org/10.1007/s00604-017-2203-6
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. https://doi.org/10.1039/C8AN02495B
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. https://doi.org/10.1039/C5AN00079C
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. https://doi.org/10.1021/cm103644b
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. https://doi.org/10.1002/jssc.201801135
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. https://doi.org/10.1016/j.apsusc.2017.03.247
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. https://doi.org/10.1021/ja900555r
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. https://doi.org/10.1007/s00604-017-2404-z
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. https://doi.org/10.1016/j.chroma.2015.01.044
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. https://doi.org/10.1016/j.chroma.2017.10.051
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. https://doi.org/10.1016/j.chroma.2015.03.046
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. https://doi.org/10.1016/j.jhazmat.2018.09.052
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. https://doi.org/10.1007/s00604-019-3694-0
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. https://doi.org/10.1007/s10337-015-3020-x
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. https://doi.org/10.1007/s00604-015-1638-x
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. https://doi.org/10.1016/j.jpba.2018.08.005
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. https://doi.org/10.1016/j.talanta.2018.02.069
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. https://doi.org/10.1016/j.talanta.2018.10.037
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. https://doi.org/10.1016/j.chroma.2019.06.039
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. https://doi.org/10.1007/s00604-017-2319-8
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.
Conflict of interest
The authors have declared no conflict of interest.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
About this article
Cite this article
Giesbers, M., Carrasco-Correa, E.J., Simó-Alfonso, E.F. et al. Hybrid monoliths with metal-organic frameworks in spin columns for extraction of non-steroidal drugs prior to their quantitation by reversed-phase HPLC. Microchim Acta 186, 759 (2019). https://doi.org/10.1007/s00604-019-3923-6
- 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