Skip to main content
SpringerLink
Log in

Magnetic porous carbon derived from a zinc-cobalt metal-organic framework: A adsorbent for magnetic solid phase extraction of flunitrazepam

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

Nanoporous carbon that contains magnetic cobalt nanoparticles (Co-NPC) was fabricated by direct carbonization of a Zn-Co bimetallic zeolitic imidazolate framework. After carbonization, the magnetic Co-NPs are well dispersed in the porous carbon matrix, with the result that the Co-NPC displays strong magnetism. The Co-NPC possesses a high specific surface area, large pore volumes and a microstructure comprised of mesopores and macropores. This results in fast molecular diffusion of the analytes along with excellent adsorption. The Co-NPC was used as a magnetic adsorbent for the enrichment of the benzodiazepine drug flunitrazepam (rohypnol) from tea and Ginger ale prior to high-resolution mass spectrometric analysis. The calibration plot is linear (with a correlation coefficient of >0.9869) in the 1 to 500 ng mL−1 concentration range. The limits of detection are 0.2 ng mL−1 for Ginger ale and 1.0 ngmL−1 for Arizona Tea samples, respectively, which is lower by about 4 orders of magnitude than those reported in the literature.

Magnetic nanoporous carbon was fabricated by direct carbonization of Zn-Co zeolitic imidazolate framework. It was used as a magnetic solid-phase extraction adsorbent for the preconcentration of flunitrazepam from beverage samples prior to its determination by high resolution mass spectrometry.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

Explore related subjects

Discover the latest articles, news and stories from top researchers in related subjects.

References

  1. Tolmacheva VV, Apyari VV, Furletov AA, Dmitrienko SG, Zolotov YA (2016) Facile synthesis of magnetic hypercrosslinked polystyrene and its application in the magnetic solid-phase extraction of sulfonamides from water and milk samples before their HPLC determination. Talanta 152:203–210

    Article  CAS  Google Scholar 

  2. Xie L, Jiang R, Zhu F, Liu H, Ouyang G (2014) Application of functionalized magnetic nanoparticals in samples preparation. Anal Bioanal Chem 406:377–399

    Article  CAS  Google Scholar 

  3. Wang C, Ma R, Wu Q, Sun M, Wang Z (2014) Magnetic porous carbon as an adsorbent for the enrichment ofchlorophenols from water and peach juice samples. J Chromatogr A 1361:60–66

    Article  CAS  Google Scholar 

  4. Wu Q, Zhao G, Feng C, Wang C, Wang Z (2011) Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples. J Chromatogr A 1218:7936–7942

    Article  CAS  Google Scholar 

  5. Torad NL, Hu M, Ishihara S, Sukegawa H, Belik AA, Imur MA, Ariga K, Sakka Y, Yamauchi Y (2014) Direct synthesis of MOF-derived nanoporous carbon with magnetic Co nanoparticles toward efficient water treatment. Small 10:2096–2107

    Article  CAS  Google Scholar 

  6. Chen Y, Wang C, Wu Z, Xiong Y, Xu Q, Yu S, Jiang H (2015) From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater 27:5010–5016

    Article  CAS  Google Scholar 

  7. Liu B, Shioyama H, Akita T, Xu Q (2008) Metal-organic framework as a template for porous carbon synthesis. J Am Chem Soc 130:5390–5391

    Article  CAS  Google Scholar 

  8. Hu M, Reboul J, Furukawa S, Torad NL, Ji Q, Srinivasu P, Ariga K, Kitagawa S, Yamauchi Y (2012) Direct carbonization of Al-based porous coordination polymer for synthesis of nanoporous carbon. J Am Chem Soc 134:2864–2867

    Article  CAS  Google Scholar 

  9. Radhakrishnan L, Reboul J, Furukawa S, Srinivasu P, Kitagawa S, Yamauchi Y (2011) Preparation of microporous carbon fibers through carbonization of Al-based porous coordination polymer (Al-PCP) with furfuryl alcohol. Chem Mater 23:1225–1231

    Article  CAS  Google Scholar 

  10. Amali AJ, Sun JK, Xu Q (2014) From assembled metal–organic framework nanoparticles to hierarchically porous carbon for electrochemical energy storage. Chem Commun 50:1519–1522

    Article  CAS  Google Scholar 

  11. Hao L, Wang C, Wu Q, Li Z, Zang X, Wang Z (2014) Metal-organic framework derived magnetic nanoporous carbon: a adsorbent for magnetic solid-phase extraction. Anal Chem 86:12199–12205

    Article  CAS  Google Scholar 

  12. Pachfule P, Biswal BP, Banerjee R (2012) Control of porosity by using isoreticular zeolitic imidazolate frameworks (IRZIFs) as a template for porous carbon synthesis. Chem Eur J 18:11399–11408

    Article  CAS  Google Scholar 

  13. Chaikittisilp W, Ariga K, Yamauchi Y (2013) A family of carbon materials: synthesis of MOF derived nanoporous carbons and their promising applications. J Mater Chem A 1:14–19

    Article  CAS  Google Scholar 

  14. Hao L, Liu X, Wang J, Wang C, Wu Q, Wang Z (2015) Use of ZIF-8-derived nanoporous carbon as the adsorbent for the solid phase extraction of carbamate pesticides prior to high-performance liquid chromatographic analysis. Talanta 142:104–109

    Article  CAS  Google Scholar 

  15. Liu X, Wang C, Wang Z, Wu Q, Wang Z (2015) Nanoporous carbon derived from a metal organic framework as a kind of adsorbent for dispersive solid phase extraction of benzoylurea insecticides. Microchim Acta 182:1903–1910

    Article  CAS  Google Scholar 

  16. Zhang X, Zang X, Wang J, Wang C, Wu Q, Wang Z (2015) Porous carbon derived from aluminum-based metal organic framework as a fiber coating for the solid-phase microextraction of polycyclic aromatic hydrocarbons from water and soil. Microchim Acta 182:2353–2359

    Article  CAS  Google Scholar 

  17. Liu X, Wang C, Wu Q, Wang Z (2015) Metal-organic framework-templated synthesis of magnetic nanoporous carbon as an efficient absorbent for enrichment of phenylurea herbicides. Anal Chim Acta 870:67–74

    Article  CAS  Google Scholar 

  18. Afsahi F, Vinh-Thang H, Mikhailenko S, Kaliaguine S (2013) Electrocatalyst synthesized from metal organic frameworks. J Power Sources 239:415–423

    Article  CAS  Google Scholar 

  19. Zhou Q, Zhu L, Xia X, Tang H (2016) The water-resistant zeolite imidazolate framework 67 is a viable solid phase sorbent for fluoroquinolones while efficiently excluding macromolecules. Microchim Acta 183:1839–1846

    Article  CAS  Google Scholar 

  20. Zhang L, Su Z, Jiang F, Yang L, Qian J, Zhou Y, Li W, Hong M (2014) Highly graphitized nitrogen-doped porous carbon nanopolyhedra derived from ZIF-8 nanocrystals as efficient electrocatalysts for oxygen reduction reactions. Nanoscale 6:6590–6602

    Article  CAS  Google Scholar 

  21. Huang C, Jen H, Wang R, Hsieh Y (2006) Sweeping technique combined with micellar electrokinetic chromatography for the simultaneous determination of flunitrazepam and its major metabolites. J Chromatogr A 1110:240–244

    Article  CAS  Google Scholar 

  22. Bai H, Lin S, Chan S, Fuh M (2010) Characterization and evaluation of two-dimensional microfluidic chip-HPLC coupled to tandem mass spectrometry for quantitative analysis of 7-aminoflunitrazepam in human urine. Analyst 135:2737–2742

    Article  CAS  Google Scholar 

  23. Staeheli SN, Poetzsch M, Kraemer T, Steuer AE (2015) Development and validation of a dynamic range-extended LC-MS/MS multi-analyte method for 11 different postmortem matrices for redistribution studies applying solvent calibration and additional 13C isotope monitoring. Anal Bioanal Chem 407:8681–8712

    Article  CAS  Google Scholar 

  24. Versace F, Sporkert F, Mangin P, Staub C (2012) Rapid sample pre-treatment prior to GC–MS and GC–MS/MS urinary toxicological screening. Talanta 101:299–306

    Article  CAS  Google Scholar 

  25. Nozawa H, Minakata K, Yamagishi I, Hasegawa K, Wurita A, Gonmori K, Suzuki O, Watanabe K (2015) MALDI-TOF mass spectrometric determination of eight benzodiazepines with two of their metabolites in blood. Legal Med 17:150–156

    Article  CAS  Google Scholar 

  26. D'Aloise P, Chen H (2012) Rapid determination of flunitrazepam in alcoholic beverages by desorption electrospray ionization-mass spectrometry. Sci Justice 52:2–8

    Article  Google Scholar 

  27. Cheng S, Wang J, Cai Y, Loo JA, Chen H (2015) Enhancing performance of liquid sample desorption electrospray ionization mass spectrometry using trap and capillary columns, inter. J. Mass Spectrom. Inter. J Mass Spectrom 392:73–79

    Article  CAS  Google Scholar 

  28. Baia TC, Gama RA, Silva de Lima LA, Lima KMG (2016) FTIR microspectroscopy coupled with variable selection methods for the identification of flunitrazepam in necrophagous flies. Anal Methods 8:968–972

    Article  CAS  Google Scholar 

  29. Shan WC, Cui YL, He X, Zhang L, Liu J, Wang JP (2015) Production of monoclonal antibody against clonazepam for immunoassay of benzodiazepine drugs in swine tissues. J Environ Sci Health, Part B 50:15–22

    Article  CAS  Google Scholar 

  30. Bermejo E, Zapardiel A, Pérez JA, Huerta A, Hernández L (1993) Voltammetric studies of a psychotropic drug with nitro groups. Determination of flunitrazepam in urine using HMDE. Talanta 40:1649–1656

    Article  CAS  Google Scholar 

  31. Glish GL, Vachet RW (2003) The basics of mass spectrometry in the twenty-first century. Nat Rev Drug Discov 2:140–150

    Article  CAS  Google Scholar 

  32. Acikkol M, Mercan S, Karadayi S (2009) Simultaneous determination of benzodiazepines and ketamine from alcoholic and nonalcoholic beverages by GC-MS in drug facilitated crimes. Chromatographia 70:1295–1298

    Article  CAS  Google Scholar 

  33. Famiglini G, Capriotti F, Palma P, Termopoli V, Cappiello A (2015) The rapid measurement of benzodiazepines in a milk-based alcoholic beverage using QuEChERS extraction and GC–MS analysis. J Anal Toxicol 39:306–310

    Article  CAS  Google Scholar 

  34. Honeychurch KC, Davidson GM, Brown E, Hart JP (2015) Reductive–reductive mode electrochemical detection of Rohypnol following liquid chromatography and its determination in coffee. Anal Chim Acta 853:222–227

    Article  CAS  Google Scholar 

  35. Famiglini G, Termopoli V, Palma P, Cappiello A (2016) Liquid chromatography-electron ionization tandem mass spectrometry with the direct-EI interface in the fast determination of diazepam and flunitrazepam in alcoholic beverages. Electrophoresis 37:1048–1054

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Financial supports from Program of Study Abroad for Young Teachers by Agricultural University of Hebei, NSF Career Award (CHE-1149367), and NSF IDBR (CHE-1455554), the National Natural Science Foundation of China (31471643, 31671930), the Natural Science Foundation of Hebei Province (B2016204136), the Scientific and Technological Research Foundation of the Department of Education of Hebei Province (ZD2016085) are gratefully acknowledged.

Author information

Authors and Affiliations

  1. Center for Intelligent Chemical Instrumentation, Department of Chemistry and Biochemistry, Edison Biotechnology Institute, Ohio University, Athens, OH, 45701, USA

    Qiuhua Wu, Si Cheng, Chenhuan Wang, Xiyang Li, Zhi Li & Chen Hao

  2. College of Science, Agricultural University of Hebei, Baoding, Hebei, 071001, China

    Qiuhua Wu & Zhi Li

  3. College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, 066004, China

    Chenhuan Wang

Authors
  1. Qiuhua Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Si Cheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chenhuan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiyang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhi Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chen Hao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Qiuhua Wu or Chen Hao.

Ethics declarations

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

Additional information

Qiuhua Wu and Si Cheng contributed equally to this work.

Electronic Supplementary Materials

ESM 1

(DOC 847 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wu, Q., Cheng, S., Wang, C. et al. Magnetic porous carbon derived from a zinc-cobalt metal-organic framework: A adsorbent for magnetic solid phase extraction of flunitrazepam. Microchim Acta 183, 3009–3017 (2016). https://doi.org/10.1007/s00604-016-1948-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-016-1948-7

Keywords

Search

Navigation