Journal of the Iranian Chemical Society

, Volume 16, Issue 1, pp 93–100 | Cite as

Risedronate extraction from artificial urine with using monolithic polymer-based anion exchangers

  • Monika ZielińskaEmail author
  • Adam Voelkel
Original Paper


Bisphosphonates are poorly sorbed from the gastrointestinal tract, therefore, the urinary recovery ratio after oral administration is an important parameter to control. Analysis of bisphosphonates in biological samples causes challenges due to their chemical properties. Their high solubility in water and extensive ionization cause that reported tedious sample extraction methods generally involved a combination of multiple extraction steps. Therefore, competitive solution to the conventional sample preparation techniques was proposed in this work. Aminated poly(styrene–divinylbenzene–vinylbenzyl chloride) monoliths and aminated poly(divinylbenzene–vinylbenzyl chloride) were prepared by in situ polymerization in stainless steel needles. Amination of polymerized monolith was carried out by trimethylamine or pyridine. Several research methods were applied to assess the modification of monolithic materials: Energy dispersive X-ray Spectrometry, scanning electron microscope images and Fourier Transform Infrared Spectroscopy. Artificial urine used as simulated body fluid containing sodium risedronate as standard compound was passed through monolithic in-needle extraction (MINE) device. The amount of analyte in eluate solutions was measured using HPLC system. The effectiveness of complete desorption process was over 95% with using potassium phosphate solution (pH 7.8) as eluent.


Adsorption Copolymers Anionic polymer synthesis Spectroscopy UV–Vis Bisphosphonate 



This study was funded by the Polish National Science Centre, Grant No. 2013/11/D/ST4/02829.

Compliance with ethical standards

Conflict of interest

The authors declare no conflicts of interest.


  1. 1.
    R. Graham, G. Russell, Bisphosphonates: the first 40 years. Bone 49, 2–19 (2011)CrossRefGoogle Scholar
  2. 2.
    E.L. George, Y.-L. Lin, M.M. Saunders, Bisphosphonate-related osteonecrosis of the jaw: a mechanobiology perspective. Bone Reports 8, 104–109 (2018)CrossRefGoogle Scholar
  3. 3.
    J.H. Lin, Bisphosphonates: a review of their pharmacokinetic properties. Bone 18, 75–85 (1996)CrossRefGoogle Scholar
  4. 4.
    S. Ghassabian, L.A. Wright, A.D. deJager, M.T. Smith, Development and validation of a sensitive solid-phase-extraction (SPE) method using high-performance liquid chromatography/tandem mass spectrometry (LC–MS/MS) for determination of risedronate concentrations in human plasma. J. Chromatogr. B 881, 34–41 (2012)CrossRefGoogle Scholar
  5. 5.
    W.F. Kline, B.K. Matuszewski, Improved determination of the bisphosphonate alendronate in human plasma and urine by automated precolumn derivatization and high-performance liquid chromatography with fluorescence and electrochemical detection. J. Chromatogr. Biomed. Appl. 583, 183–193 (1992)CrossRefGoogle Scholar
  6. 6.
    C.K. Zacharis, P.D. Tzanavaras, Determination of bisphosphonate active pharmaceutical ingredients in pharmaceuticals and biological material: a review of analytical methods. J. Pharm. Biomed. Anal. 48, 483–496 (2008)CrossRefGoogle Scholar
  7. 7.
    R.W. Sparidans, J. Den Hartigh, S. Cremers, J.H. Beijnen, P. Vermeij, Semi-automatic liquid chromatographic analysis of olpadronate in urine and serum using derivatization with (9-fluorenylmethyl) chloroformate. J. Chromatogr. B Biomed. Sci. Appl. 738, 331–341 (2000)CrossRefGoogle Scholar
  8. 8.
    H.J. Leis, G. Fauler, W. Windischhofer, Use of 18O3-clodronate as an internal standard for the quantitative analysis of clodronate in human plasma by gas chromatography/electron ionisation mass spectrometry. Rapid Commun. Mass Spectrom. 18, 2781–2784 (2004)CrossRefGoogle Scholar
  9. 9.
    M.J. Lovdah, D.J. Pietrzyk, Anion-exchange separation and determination of bisphosphonates and related analytes by post-column indirect fluorescence detection. J. Chromatogr. A 850, 143–152 (1999)CrossRefGoogle Scholar
  10. 10.
    M. Pietrzyńska, A. Voelkel, K. Bielicka-Daszkiewicz, Preparation and examination of monolithic in-needle extraction (MINE) device for the direct analysis of liquid samples. Anal. Chim. Acta 776, 50–56 (2013)CrossRefGoogle Scholar
  11. 11.
    M. Pietrzyńska, K. Adamska, M. Szubert, A. Voelkel, Solubility parameter used to predict the effectiveness of monolithic in-needle extraction (MINE) device for the direct analysis of liquid samples. Anal. Chim. Acta 805, 54–59 (2013)CrossRefGoogle Scholar
  12. 12.
    M. Pietrzyńska, A. Voelkel, Optimization of the in-needle extraction device for the direct flow of the liquid sample through the sorbent layer. Talanta 129, 392–397 (2014)CrossRefGoogle Scholar
  13. 13.
    K. Kędziora, W. Wasiak, Extraction media used in needle trap devices—progress in development and application. J. Chromatogr. A 1505, 1–17 (2017)CrossRefGoogle Scholar
  14. 14.
    M. Pietrzyńska, R. Brożek, A. Voelkel, R. Koczorowski, In-needle extraction technique in determination of organic compounds released from dental tissue conditioners incubated in artificial saliva. Talanta 129, 203–208 (2014)CrossRefGoogle Scholar
  15. 15.
    Tong s., Liu S., H. Wang, Q. Jia, Recent advances of polymer monolithic columns functionalized with micro/nanomaterials: synthesis and application. Chromatographia 77, 5–14 (2014). CrossRefGoogle Scholar
  16. 16.
    N. Barlık, B. Keskinler, M.M. Kocakerim, G. Akay, Surface modification of monolithic PolyHIPE polymers for anionic functionality and their ion exchange behavior. J. Appl. Polym. Sci 132, 42286–42293 (2015)Google Scholar
  17. 17.
    H.A. Ezzeldin, A. Apblett, G.L. Foutch, Synthesis and properties of anion exchangers derived from chloromethyl styrene codivinylbenzene and their use in water treatment. Int. J. Polym. Sci. (2010).
  18. 18.
    M. Pietrzyńska, R. Tomczak, K. Jezierska, A. Voelkel, J. Jampílek, Polymer-ceramic monolithic in-needle extraction (MINE) device: preparation and examination of drug affinity. Mater. Sci. Eng. C 68, 70–77 (2016)CrossRefGoogle Scholar
  19. 19.
    L. Liu, L. Shou, H. Yu, J. Yao, Mechanical Properties and corrosion resistance of vulcanized silicone rubber after exposure to artificial urine. J. Macromol. Sci. Part B 54, 962–974 (2015)CrossRefGoogle Scholar
  20. 20.
    M. Pietrzyńska, A. Voelkel, Stability of simulated body fluids such as blood plasma, artificial urine and artificial saliva. Microchem. J. 134, 197–201 (2017)CrossRefGoogle Scholar
  21. 21.
    D.B. Rorabacher, Statistical treatment for rejection of deviant values: critical values of Dixon’s “Q” parameter and related subrange ratios at the 95% confidence level. Anal. Chem. 63, 139–146 (1991)CrossRefGoogle Scholar

Copyright information

© Iranian Chemical Society 2018

Authors and Affiliations

  1. 1.Institute of Chemical Technology and EngineeringPoznań University of TechnologyPoznanPoland

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