Advertisement

Microchimica Acta

, 186:165 | Cite as

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

  • Sze Chieh Tan
  • Hian Kee LeeEmail author
Original Paper

Abstract

A seamless two-step extraction procedure integrating ultrasound-assisted emulsification microextraction (USAEME) and vortex-assisted micro-solid-phase extraction (μ-SPE) was developed. A highly porous metal-organic framework of type MIL-101(Cr) is used as the sorbent, and ultra-high-performance liquid chromatography in combination with tandem mass spectrometry is used for detection. The steroid hormones estrone 17β-estradiol, estriol, and 17α-ethynylestradiol were extracted from water samples by using this method. These steroids are polar and do not pass through the polypropylene membrane that is conventionally used in μ-SPE. In the method presented here, 1-octanol is used in USAEME to extract and pre-concentrate the steroids. This facilitates the transfer to the MIL-101(Cr) phase retained by the membrane in the subsequent μ-SPE step. MIL-101(Cr) was characterized by various methods, and the parameters affecting the overall extraction efficiency were optimized. Under the most favorable conditions, the limits of detection are between 0.95 and 23 ng L−1. Good intra-day and inter-day precisions were obtained, with relative standard deviations of ≤ 9.9%. Enrichment factors are between 34 and 52. The method was applied to genuine environmental water samples in which estrone was detected. Relative recoveries ranged between 85.4% and 120.8%.

Graphical abstract

Schematic of the emulsification-assisted micro-solid-phase extraction (μ-SPE). By emulsifying 1-octanol in the water sample, polar estrogens dissolved in the solvent can easily pass the hydrophobic polypropylene membrane and then are adsorbed onto the unmodified MIL-101(Cr) held within the μ-SPE device.

Keywords

Porous material Sample preparation Microextraction Membrane-protected Liquid chromatography-tandem mass spectrometry Endocrine disrupting compounds Hormones Environmental water 

Notes

Acknowledgements

The authors thankfully acknowledge the National University of Singapore (NUS) for the support provided throughout the duration of this research (Grant No. 143-000-023-001). S.C. Tan is grateful to the NUS Graduate School for Integrative Sciences and Engineering for a scholarship award.

Compliance with ethical standards

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

Supplementary material

604_2019_3289_MOESM1_ESM.docx (1.7 mb)
ESM 1 (DOCX 1703 kb)

References

  1. 1.
    Giulivo M, Lopez de Alda M, Capri E, Barcelo D (2016) Human exposure to endocrine disrupting compounds: their role in reproductive systems, metabolic syndrome and breast cancer. A review. Environ Res 151:251–264.  https://doi.org/10.1016/j.envres.2016.07.011 CrossRefPubMedGoogle Scholar
  2. 2.
    Aris AZ, Shamsuddin AS, Praveena SM (2014) Occurrence of 17alpha-ethynylestradiol (EE2) in the environment and effect on exposed biota: a review. Environ Int 69:104–119.  https://doi.org/10.1016/j.envint.2014.04.011 CrossRefPubMedGoogle Scholar
  3. 3.
    Adeel M, Song X, Wang Y, Francis D, Yang Y (2017) Environmental impact of estrogens on human, animal and plant life: a critical review. Environ Int 99:107–119.  https://doi.org/10.1016/j.envint.2016.12.010 CrossRefPubMedGoogle Scholar
  4. 4.
    Arnold KE, Brown AR, Ankley GT, Sumpter JP (2014) Medicating the environment: assessing risks of pharmaceuticals to wildlife and ecosystems. Philos Trans R Soc B 369(1656):1–11.  https://doi.org/10.1098/rstb.2013.0569 CrossRefGoogle Scholar
  5. 5.
    Salla RF, Gamero FU, Rissoli RZ, Dal-Medico SE, Castanho LM, Carvalho Cdos S, Silva-Zacarin EC, Kalinin AL, Abdalla FC, Costa MJ (2016) Impact of an environmental relevant concentration of 17alpha-ethinylestradiol on the cardiac function of bullfrog tadpoles. Chemosphere 144:1862–1868.  https://doi.org/10.1016/j.chemosphere.2015.10.042 CrossRefPubMedGoogle Scholar
  6. 6.
    Regueiro J, Llompart M, Garcia-Jares C, Garcia-Monteagudo JC, Cela R (2008) Ultrasound-assisted emulsification-microextraction of emergent contaminants and pesticides in environmental waters. J Chromatogr A 1190(1–2):27–38.  https://doi.org/10.1016/j.chroma.2008.02.091 CrossRefPubMedGoogle Scholar
  7. 7.
    Guo L, Lee HK (2014) Automated dispersive liquid-liquid microextraction-gas chromatography-mass spectrometry. Anal Chem 86(8):3743–3749.  https://doi.org/10.1021/ac404088c CrossRefPubMedGoogle Scholar
  8. 8.
    Basheer C, Alnedhary AA, Rao BSM, Valliyaveettil S, Lee HK (2006) Development and application of porous membrane-protected carbon nanotube micro-solid-phase extraction combined with gas chromatography/mass spectrometry. Anal Chem 78:2853–2858.  https://doi.org/10.1021/ac060240i CrossRefPubMedGoogle Scholar
  9. 9.
    Kanimozhi S, Basheer C, Narasimhan K, Liu L, Koh S, Xue F, Choolani M, Lee HK (2011) Application of porous membrane protected micro-solid-phase-extraction combined with gas chromatography-mass spectrometry for the determination of estrogens in ovarian cyst fluid samples. Anal Chim Acta 687(1):56–60.  https://doi.org/10.1016/j.aca.2010.12.007 CrossRefPubMedGoogle Scholar
  10. 10.
    Khayoon WS, Saad B, Salleh B, Manaf NH, Latiff AA (2014) Micro-solid phase extraction with liquid chromatography-tandem mass spectrometry for the determination of aflatoxins in coffee and malt beverage. Food Chem 147:287–294.  https://doi.org/10.1016/j.foodchem.2013.09.049 CrossRefPubMedGoogle Scholar
  11. 11.
    Huang Z, Lee HK (2015) Micro-solid-phase extraction of organochlorine pesticides using porous metal-organic framework MIL-101 as sorbent. J Chromatogr A 1401:9–16.  https://doi.org/10.1016/j.chroma.2015.04.052 CrossRefPubMedGoogle Scholar
  12. 12.
    Jiang T, Zhao L, Chu B, Feng Q, Yan W, Lin JM (2009) Molecularly imprinted solid-phase extraction for the selective determination of 17beta-estradiol in fishery samples with high performance liquid chromatography. Talanta 78(2):442–447.  https://doi.org/10.1016/j.talanta.2008.11.047 CrossRefPubMedGoogle Scholar
  13. 13.
    Zhu H, Chen W, Li Z, He J, Tang X, Wang C (2014) Extraction of natural estrogens in environmental waters by dispersive multiwalled carbon nanotube-based agitation-assisted adsorption and ultrasound-assisted desorption. Anal Methods 6(4):1235–1241.  https://doi.org/10.1039/c3ay41799a CrossRefGoogle Scholar
  14. 14.
    Huang Z, Lee HK (2015) Performance of metal-organic framework MIL-101 after surfactant modification in the extraction of endocrine disrupting chemicals from environmental water samples. Talanta 143:366–373.  https://doi.org/10.1016/j.talanta.2015.05.006 CrossRefPubMedGoogle Scholar
  15. 15.
    Huang YF, Liu M, Wang YQ, Li Y, Zhang JM, Huo SH (2016) Hydrothermal synthesis of functionalized magnetic MIL-101 for magnetic enrichment of estrogens in environmental water samples. RSC Adv 6(19):15362–15369.  https://doi.org/10.1039/c5ra23132a CrossRefGoogle Scholar
  16. 16.
    Li H, Eddaoudi M, O'Keeffe M, Yaghi OM (1999) Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature 402:276–279.  https://doi.org/10.1038/46248 CrossRefGoogle Scholar
  17. 17.
    Zhou HC, Long JR, Yaghi OM (2012) Introduction to metal-organic frameworks. Chem Rev 112(2):673–674.  https://doi.org/10.1021/cr300014x CrossRefPubMedGoogle Scholar
  18. 18.
    Peng J, Tian H, Du Q, Hui X, He H (2018) A regenerable sorbent composed of a zeolite imidazolate framework (ZIF-8), Fe3O4 and graphene oxide for enrichment of atorvastatin and simvastatin prior to their determination by HPLC. Microchim Acta 185(2):141.  https://doi.org/10.1007/s00604-018-2697-6 CrossRefGoogle Scholar
  19. 19.
    Lv F, Gan N, Huang J, Hu F, Cao Y, Zhou Y, Dong Y, Zhang L, Jiang S (2017) A poly-dopamine based metal-organic framework coating of the type PDA-MIL-53(Fe) for ultrasound-assisted solid-phase microextraction of polychlorinated biphenyls prior to their determination by GC-MS. Microchim Acta 184(8):2561–2568.  https://doi.org/10.1007/s00604-017-2208-1 CrossRefGoogle Scholar
  20. 20.
    Férey G, Mellot-Draznieks C, Serre C, Millange F, Dutour J, Surblé S, Margiolaki I (2005) A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 309:2040–2042.  https://doi.org/10.1126/science.1116275 CrossRefPubMedGoogle Scholar
  21. 21.
    Zang X, Zhang G, Chang Q, Zhang X, Wang C, Wang Z (2015) Metal organic framework MIL-101 coated fiber for headspace solid phase microextraction of volatile aromatic compounds. Anal Methods 7(3):918–923.  https://doi.org/10.1039/c4ay02540g CrossRefGoogle Scholar
  22. 22.
    Gu ZY, Jiang DQ, Wang HF, Cui XY, Yan XP (2010) Adsorption and separation of xylene isomers and ethylbenzene on two Zn-terephthalate metal-organic frameworks. J Phys Chem C 114:311–316CrossRefGoogle Scholar
  23. 23.
    Yang CX, Yan XP (2011) Metal-organic framework MIL-101(Cr) for high-performance liquid chromatographic separation of substituted aromatics. Anal Chem 83(18):7144–7150.  https://doi.org/10.1021/ac201517c CrossRefPubMedGoogle Scholar
  24. 24.
    Kalantari H, Manoochehri M (2018) A nanocomposite consisting of MIL-101(Cr) and functionalized magnetite nanoparticles for extraction and determination of selenium(IV) and selenium(VI). Microchim Acta 185(3):196.  https://doi.org/10.1007/s00604-018-2731-8 CrossRefGoogle Scholar
  25. 25.
    He X, Yang W, Li S, Liu Y, Hu B, Wang T, Hou X (2018) An amino-functionalized magnetic framework composite of type Fe3O4-NH2@MIL-101(Cr) for extraction of pyrethroids coupled with GC-ECD. Microchim Acta 185(2):125.  https://doi.org/10.1007/s00604-018-2672-2 CrossRefGoogle Scholar
  26. 26.
    Wang T, Liu S, Gao G, Zhao P, Lu N, Lun X, Hou X (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):2981–2990.  https://doi.org/10.1007/s00604-017-2319-8 CrossRefGoogle Scholar
  27. 27.
    Li N, Wang Z, Zhang L, Nian L, Lei L, Yang X, Zhang H, Yu A (2014) Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction of herbicides in peanuts. Talanta 128:345–353.  https://doi.org/10.1016/j.talanta.2014.04.084 CrossRefPubMedGoogle Scholar
  28. 28.
    Gao G, Li S, Li S, Zhao L, Wang T, Hou X (2018) Development and application of vortex-assisted membrane extraction based on metal-organic framework mixed-matrix membrane for the analysis of estrogens in human urine. Anal Chim Acta 1023:35–43.  https://doi.org/10.1016/j.aca.2018.04.013 CrossRefPubMedGoogle Scholar
  29. 29.
    Wee LH, Bonino F, Lamberti C, Bordiga S, Martens JA (2014) Cr-MIL-101 encapsulated Keggin phosphotungstic acid as active nanomaterial for catalysing the alcoholysis of styrene oxide. Green Chem 16(3):1351–1357.  https://doi.org/10.1039/c3gc41988f CrossRefGoogle Scholar
  30. 30.
    Hu J, Zhang H, Chang H (2005) Improved method for analyzing estrogens in water by liquid chromatography–electrospray mass spectrometry. J Chromatogr A 1070(1–2):221–224.  https://doi.org/10.1016/j.chroma.2005.02.069 CrossRefPubMedGoogle Scholar
  31. 31.
    Sadowski R, Gadzala-Kopciuch R (2013) Isolation and determination of estrogens in water samples by solid-phase extraction using molecularly imprinted polymers and HPLC. J Sep Sci 36(14):2299–2305.  https://doi.org/10.1002/jssc.201300366 CrossRefPubMedGoogle Scholar
  32. 32.
    Wang Y, Jin S, Wang Q, Lu G, Jiang J, Zhu D (2013) Zeolitic imidazolate framework-8 as sorbent of micro-solid-phase extraction to determine estrogens in environmental water samples. J Chromatogr A 1291:27–32.  https://doi.org/10.1016/j.chroma.2013.03.032 CrossRefPubMedGoogle Scholar
  33. 33.
    Hu C, He M, Chen B, Zhong C, Hu B (2013) Polydimethylsiloxane/metal-organic frameworks coated stir bar sorptive extraction coupled to high performance liquid chromatography-ultraviolet detector for the determination of estrogens in environmental water samples. J Chromatogr A 1310:21–30.  https://doi.org/10.1016/j.chroma.2013.08.047 CrossRefPubMedGoogle Scholar
  34. 34.
    Wang L, Cai YQ, He B, Yuan CG, Shen DZ, Shao J, Jiang GB (2006) Determination of estrogens in water by HPLC-UV using cloud point extraction. Talanta 70(1):47–51.  https://doi.org/10.1016/j.talanta.2006.01.013 CrossRefPubMedGoogle Scholar
  35. 35.
    Goh SX, Lee HK (2017) An alternative perspective of hollow fiber-mediated extraction: bundled hollow fiber array-liquid-phase microextraction with sonication-assisted desorption and liquid chromatography-tandem mass spectrometry for determination of estrogens in aqueous matrices. J Chromatogr A 1488:26–36.  https://doi.org/10.1016/j.chroma.2017.01.081 CrossRefPubMedGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.NUS Graduate School for Integrative Sciences and EngineeringNational University of SingaporeSingaporeSingapore
  2. 2.Department of ChemistryNational University of SingaporeSingaporeSingapore
  3. 3.National University of Singapore Environmental Research InstituteSingaporeSingapore

Personalised recommendations