Microchimica Acta

, 186:827 | Cite as

Magnetic covalent organic frameworks with core-shell structure as sorbents for solid phase extraction of fluoroquinolones, and their quantitation by HPLC

  • Min Wang
  • Manjie Gao
  • Kailian Zhang
  • Lujun Wang
  • Wencheng Wang
  • Qifeng FuEmail author
  • Zhining Xia
  • Die GaoEmail author
Original Paper


A core-shell structured magnetic covalent organic frameworks of the type Fe3O4@COFs was prepared by using the Fe3O4 nanoparticles as magnetic core, and 4,4”-diamino-p-terphenyl and 1,3,5-tris(p-formylphenyl)benzene as two building blocks. The Fe3O4@COFs were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive spectrum, Fourier transform infrared spectroscopy, zeta potentiometric analysis, X-ray diffraction, vibrating sample magnetometry, thermogravimetric analysis and the nitrogen adsorption-desorption isotherms. The Fe3O4@COFs have core-shell structure with average diameter of 200 ± 2.4 nm, a high specific surface area (124 m2·g-1), uniform pore size distribution (3.1 nm), good magnetic responsivity (36.8 emu·g-1), good thermal and chemical stability. They were applied as the sorbents for magnetic solid phase extraction (MSPE) for fluoroquinolones (FQs) ciprofloxacin, enrofloxacin, lomefloxacin, gatifloxacin, levofloxacin and pefloxacin. The effects of sorbent dosage, extraction time, p H value, ionic strength, desorption solvent and desorption time were investigated. By combining MSPE with HPLC-DAD analysis, a rapid and sensitive method was developed for the enrichment and determination of these FQs. The method had good linearity in the range of 2.5-1500 ng·g-1 FQ concentration range and low limits of detection (0.25-0.5 ng·g-1). The method was successfully applied to the extraction and determination of FQs in (spiked) pork, milk and human plasma samples. Recoveries ranged from 78.7-103.5% (with RSD<6.2%).

Graphical abstract

Schematic representation of the magnetic covalent organic frameworks which prepared by using the Fe3O4 nanoparticles as magnetic core, 4,4”-diamino-p-terphenyl and 1,3,5-tris(p-formylphenyl)benzene as two building blocks. The Fe3O4@COFs were applied as adsorbents for magnetic solid phase extraction of six fluoroquinolones (FQs) and HPLC-DAD was applied to analysis the extraction efficiencies.


Covalent organic framework Fluoroquinolones residues Complex samples Sample pretreatment Magnetic solid phase extraction Sorbents 



This work was supported by the National Natural Science Foundation of China (No. 21904109), the university level fund of Southwest medical university (NO. 2017-ZRQN-032) and the joint program of Luzhou government-Southwest medical university (NO. 2015LZCYD-S07(2/5)).

Compliance with ethical standards

Conflict of interest

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

Supplementary material

604_2019_3757_MOESM1_ESM.docx (1.1 mb)
ESM 1 (DOCX 1.04 mb)


  1. 1.
    Liu YZ, Ma YH, Zhao YB, Sun XX, Gandara F, Furukawa H (2016) Weaving of organic threads into a crystalline covalent organic framework. Science 351:365–369. CrossRefPubMedGoogle Scholar
  2. 2.
    Fang QR, Wang JH, Gu S, Kaspar RB, Zhuang ZB, Zheng J (2015) 3D Porous Crystalline Polyimide Covalent Organic Frameworks for Drug Delivery. J Am Chem Soc 137:8352–8355. CrossRefPubMedGoogle Scholar
  3. 3.
    Zhang X, Wang Z, Yao L, Mai YY, Liu JQ, Hua XL (2018) Synthesis of core-shell covalent organic frameworks/multi-walled carbon nanotubes nanocomposite and application in lithium-sulfur batteries. Mater Lett 213:143–147. CrossRefGoogle Scholar
  4. 4.
    Li N, Du JJ, Wu D, Liu JC, Li N, Sun ZW (2018) Recent advances in facile synthesis and applications of covalent organic framework materials as superior sorbents in sample pretreatment. Trac-Trend Anal Chem 108:154–166. CrossRefGoogle Scholar
  5. 5.
    Salonen LM, Pinela SR, Fernandes SPS, Loucano J, Carbo-Argibay E, Sarria MP (2017) Adsorption of marine phycotoxin okadaic acid on a covalent organic framework. J Chromatogr A 1525:17–22. CrossRefPubMedGoogle Scholar
  6. 6.
    Li SF, Yang YH, Shan HC, Zhao J, Wang Z, Cai D (2019) Ultrafast and ultrahigh adsorption of furfural from aqueous solution via covalent organic framework-300. Sep Purif Technol 220:283–292. CrossRefGoogle Scholar
  7. 7.
    Li N, Wu D, Liu JC, Hu N, Shi XX, Dai CJ (2018) Magnetic covalent organic frameworks based on magnetic solid phase extraction for determination of six steroidal and phenolic endocrine disrupting chemicals in food samples. Microchem J 143:350–358. CrossRefGoogle Scholar
  8. 8.
    Chen L, He YT, Lei ZX, Gao CL, Xie Q, Tong P (2018) Preparation of core-shell structured magnetic covalent organic framework nanocomposites for magnetic solid-phase extraction of bisphenols from human serum sample. Talanta 181:296–304. CrossRefPubMedGoogle Scholar
  9. 9.
    Chen L, Zhang MY, Fu FF, Li JG, Lin Z (2018) Facile synthesis of magnetic covalent organic framework nanobeads and application to magnetic solid-phase extraction of trace estrogens from human urine. J Chromatogr A 1567:136–146. CrossRefGoogle Scholar
  10. 10.
    Ren JY, Wang XL, Li XL, Wang ML, Zhao RS, Lin JM (2018) Magnetic covalent triazine-based frameworks as magnetic solid-phase extraction sorbents for sensitive determination of perfluorinated compounds in environmental water samples. Anal Bioanal Chem 410:1657–1665. CrossRefPubMedGoogle Scholar
  11. 11.
    Pinacho DG, Sanchez-Baeza F, Marco MP (2012) Molecular modeling assisted hapten design to produce broad selectivity antibodies for fluoroquinolone antibiotics. Anal Chem 84:4527–4534. CrossRefPubMedGoogle Scholar
  12. 12.
    Hua JH, Jiao Y, Wang M, Yang YL (2018) Determination of norfloxacin or ciprofloxacin by carbon dots fluorescence enhancement using magnetic nanoparticles as sorbents. Microchim Acta 185.
  13. 13.
    Kummerer K (2009) The presence of pharmaceuticals in the environment due to human use - present knowledge and future challenges. J Environ Manag 90:2354–2366. CrossRefGoogle Scholar
  14. 14.
    Wu H, Liu YL, Chang JZ, Zhao BX, Huo YX, Wang ZL (2019) Extraction of Five Fluoroquinolones in Eggs by Magnetic Solid-Phase Extraction with Fe3O4-MoS2 and Determination by HPLC-UV. Food Anal Methods 12:712–721. CrossRefGoogle Scholar
  15. 15.
    Wang Y, Tong Y, Xu X, Zhang L (2018) Metal-organic framework-derived three-dimensional porous graphitic octahedron carbon cages-encapsulated copper nanoparticles hybrids as highly efficient enrichment material for simultaneous determination of four fluoroquinolones. J Chromatogr A 533:1–9. CrossRefGoogle Scholar
  16. 16.
    Zhou XT, Wang LM, Shen GQ, Zhang DW, Xie JL, Mamut A (2018) Colorimetric determination of ofloxacin using unmodified aptamers and the aggregation of gold nanoparticles. Microchim Acta 185.
  17. 17.
    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. CrossRefPubMedGoogle Scholar
  18. 18.
    Wang HX, Ren LS, Yu X, Hu J, Chen Y, He GS (2017) Antibiotic residues in meat, milk and aquatic products in Shanghai and human exposure assessment. Food Control 80:217–225. CrossRefGoogle Scholar
  19. 19.
    Blanca-Lopez N, Ariza A, Dona I, Mayorga C, Montanez MI, Garcia-Campos J (2013) Hypersensitivity reactions to fluoroquinolones: analysis of the factors involved. Clin Exp Allergy 43:560–567. CrossRefPubMedGoogle Scholar
  20. 20.
    Liu HH (2010) Safety Profile of the Fluoroquinolones Focus on Levofloxacin. Drug Saf 33:353–369. CrossRefPubMedGoogle Scholar
  21. 21.
    Drlica K, Mustaev A, Towle TR, Luan G, Kerns RJ, Berger JM (2014) Bypassing fluoroquinolone resistance with quinazolinediones: Studies of drug-gyrase-DNA complexes having implications for drug design. ACS Chem Biol 9:2895–2904. CrossRefPubMedPubMedCentralGoogle Scholar
  22. 22.
    Wang R, Chen ZL (2017) A covalent organic framework-based magnetic sorbent for solid phase extraction of polycyclic aromatic hydrocarbons, and its hyphenation to HPLC for quantitation. Microchim Acta 184:3867–3874. CrossRefGoogle Scholar
  23. 23.
    Gao Q, Zheng HB, Luo D, Ding J, Feng YQ (2012) Facile synthesis of magnetic one-dimensional polyaniline and its application in magnetic solid phase extraction for fluoroquinolones in honey samples. Anal Chim Acta 720:57–62. CrossRefPubMedGoogle Scholar
  24. 24.
    Amoli-Diva M, Pourghazi K, Hajjaran S (2016) Dispersive micro-solid phase extraction using magnetic nanoparticle modified multi-walled carbon nanotubes coupled with surfactant-enhanced spectrofluorimetry for sensitive determination of lomefloxacin and ofloxacin from biological samples. Mat Sci Eng C-Mater 60:30–36. CrossRefGoogle Scholar
  25. 25.
    Wang YF, Wang YG, Ouyang XK, Yang LY (2017) Surface-imprinted magnetic carboxylated cellulose nanocrystals for the highly selective extraction of six fluoroquinolones from egg samples. ACS Appl Mater Interfaces 9:1759–1769. CrossRefPubMedGoogle Scholar
  26. 26.
    Wang Q, Wang Y, Zhang Z, Tong Y, Zhang L (2017) Waxberry-like magnetic porous carbon composites prepared from a nickel-organic framework for solid-phase extraction of fluoroquinolones. Microchim Acta 184:4107–4115. CrossRefGoogle Scholar
  27. 27.
    Speltini A, Sturini M, Maraschi F, Mandelli E, Vadivel D, Dondi D (2016) Preparation of silica-supported carbon by Kraft lignin pyrolysis, and its use in solid-phase extraction of fluoroquinolones from environmental waters. Microchim Acta 183:2241–2249. CrossRefGoogle Scholar
  28. 28.
    Lavaee P, Danesh NM, Ramezani M, Abnous K, Taghdisi SM (2017) Colorimetric aptamer based assay for the determination of fluoroquinolones by triggering the reduction-catalyzing activity of gold nanoparticles. Microchim Acta 184:2039–2045. CrossRefGoogle Scholar
  29. 29.
    Liu J, Sun Z, Deng Y, Zou Y, Li C, Guo X (2009) Highly water-dispersible biocompatible magnetite particles with low cytotoxicity stabilized by citrate groups. Angew Chem Int Ed 48:5875–5879. CrossRefGoogle Scholar
  30. 30.
    Deng ZH, Wang X, Wang XL, Gao CL, Dong L, Wang ML (2019) A core-shell structured magnetic covalent organic framework (type Fe3O4@COF) as a sorbent for solid-phase extraction of endocrine-disrupting phenols prior to their quantitation by HPLC. Microchim Acta 186:108. CrossRefGoogle Scholar
  31. 31.
    Li N, Wu D, Hu N, Fan G, Li X, Sun J (2018) Effective Enrichment and Detection of Trace Polycyclic Aromatic Hydrocarbons in Food Samples based on Magnetic Covalent Organic Framework Hybrid Microspheres. J Agric Food Chem 66:3572–3580. CrossRefPubMedGoogle Scholar
  32. 32.
    Lin G, Gao C, Zheng Q, Lei Z, Geng H, Lin Z (2017) Room-temperature synthesis of core-shell structured magnetic covalent organic frameworks for efficient enrichment of peptides and simultaneous exclusion of proteins. Chem Commun 53:3649–3652. CrossRefGoogle Scholar
  33. 33.
    Xu LR, Zhou X, Yu YX, Tian WQ, Ma J, Lei SB (2013) Surface-confined crystalline two-dimensional covalent organic frameworks via on-surface schiff-base coupling. ACS Nano 7:8066–8073. CrossRefPubMedGoogle Scholar
  34. 34.
    Xie X, Ma X, Guo L, Fan Y, Zeng G, Zhang M (2019) Novel magnetic multi-templates molecularly imprinted polymer for selective and rapid removal and detection of alkylphenols in water. Chem Eng J 357:56–65. CrossRefGoogle Scholar
  35. 35.
    Li WX, Chen N, Zhu Y, Shou D, Zhi MY, Zeng XQ (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.
  36. 36.
    Li F, Lu L, Gao D, Wang M, Wang D, Xia Z (2018) Rapid synthesis of three-dimensional sulfur-doped porous graphene via solid-state microwave irradiation for protein removal in plasma sample pretreatment. Talanta 185:528–536. CrossRefPubMedGoogle Scholar
  37. 37.
    Song Y, Ma R, Jiao C, Hao L, Wang C, Wu Q (2017) Magnetic mesoporous polymelamine-formaldehyde resin as an sorbents for endocrine disrupting chemicals. Microchim Acta 185:19. CrossRefGoogle Scholar
  38. 38.
    Wang N, Wang YF, Omer AM, Ouyang XK (2017) Fabrication of novel surface-imprinted magnetic graphene oxide-grafted cellulose nanocrystals for selective extraction and fast adsorption of fluoroquinolones from water. Anal Bioanal Chem 409:6643–6653. CrossRefPubMedGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.School of PharmacySouthwest Medical UniversityLuzhouChina
  2. 2.School of Pharmaceutical SciencesChongqing UniversityChongqingChina
  3. 3.College of integrated Chinese and Western MedicineSouthwest Medical UniversityLuzhouChina

Personalised recommendations