Skip to main content
Log in

Spin-column micro-solid phase extraction of chlorophenols using MFU-4l metal-organic framework

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

Abstract

A novel metal-organic framework called MFU-4 l was synthesized from ZnCl2 and 1H-1,2,3-triazolo[4,5-b][4′,5′-i])dibenzo[1,4]dioxin. MFU-4 l was characterized and is shown to be a viable sorbent for spin-column micro-solid phase extraction of 4-chlorophenol, 2,3-dichlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Following extraction and elution with methanol, the chlorophenols were quantified by a GC-MS instrument. Various parameters affecting adsorption and desorption were optimized by the one variable at-a-time method. The main feature of the utilized metal-organic framework is its outstanding performance in ultratrace extraction of the target analytes due to the different amino groups existed in the linker structure. Under optimal conditions, the calibration plots are linear in the 0.5–400 μg kg−1 concentration range for water samples, and from 1.0–400 μg kg−1 for soil samples. The respective limits of detection are 0.10 and 0.50 μg kg-1 for water and soil samples, respectively. On top of that, limits of detections are lower than 0.10 and 0.50 μg Kg−1 for water and soil samples, respectively. Inter-day and intra-day relative standard deviations were in the range of 4.4–7.8% for the selected chlorophenols. Preconcentration factors are in the range of 26.3–29.6 for aqueous samples. The method was used to analyze soil and environmental water samples.

Schematic representation of spin-column micro-solid phase extraction of chlorophenols using the MFU-4 l metal-organic framework.

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

Access this article

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. García-Valverde MT, Lucena R, Cárdenas S, Valcárcel M (2016) In-syringe dispersive micro-solid phase extraction using carbon fibres for the determination of chlorophenols in human urine by gas chromatography/mass spectrometry. J Chromatogr A 1464:42–49

    Article  Google Scholar 

  2. Shi L, Wang J, Feng J, Zhao S, Wang Z, Tao H, Liu S (2017) Determination of chlorophenols in water using dispersive liquid–liquid microextraction coupled with water-in-oil microemulsion electrokinetic chromatography in normal stacking mode. J Sep Sci 40:2662–2670

    Article  CAS  Google Scholar 

  3. Wang X, Du T, Wang J, Kou H, Du X, Lu X (2018) Assessment of graphene aerogel matrix solid-phase dispersion as sample preparation for the determination of chlorophenols in soil. New J Chem 42:6778–6784

    Article  CAS  Google Scholar 

  4. Wang Y, Ma R, Xiao R, Hao L, Wu Q, Wang C, Wang Z (2018) A hyper-cross linked polymer as an adsorbent for the extraction of chlorophenols. Microchim Acta 185:108

    Article  Google Scholar 

  5. Zang X, Chang Q, Liang W, Wu T, Wang C, Wang Z (2018) Micro-solid phase extraction of chlorophenols using reduced graphene oxide functionalized with magnetic nanoparticles and graphitic carbon nitride as the adsorbent. Microchim Acta 185:18

    Article  Google Scholar 

  6. Vlastos D, Antonopoulou M, Konstantinou I (2016) Evaluation of toxicity and genotoxicity of 2-chlorophenol on bacteria, fish and human cells. Sci Total Environ 551:649–655

    Article  Google Scholar 

  7. Fan C, Li N, Cao X (2015) Determination of chlorophenols in red wine using ionic liquid countercurrent chromatography as a new pretreatment method followed by high-performance liquid chromatography. J Sep Sci 38:2109–2116

    Article  CAS  Google Scholar 

  8. Izanloo M, Esrafili A, Behbahani M, Ghambarian M, Reza Sobhi H (2018) Trace quantification of selected sulfonamides in aqueous media by implementation of a new dispersive solid-phase extraction method using a nanomagnetic titanium dioxide graphene-based sorbent and HPLC-UV. J Sep Sci 41:910–917

    Article  CAS  Google Scholar 

  9. Behbahani M, Bagheri S, Omidi F, Amini MM (2018) An amino-functionalized mesoporous silica (KIT-6) as a sorbent for dispersive and ultrasonication-assisted micro solid phase extraction of hippuric acid and methylhippuric acid, two biomarkers for toluene and xylene exposure. Microchim Acta 185:505

    Article  Google Scholar 

  10. Chen Y, Guo Z, Wang X, Qiu C (2008) Sample preparation. J Chromatogr A 1184:191–219

    Article  CAS  Google Scholar 

  11. Smith RM (2003) Before the injection—modern methods of sample preparation for separation techniques. J Chromatogr A 1000:3–27

    Article  CAS  Google Scholar 

  12. Saito Y, Kawazoe M, Imaizumi M, Morishima Y, Nakao Y, Hatano K, Hayashida M, Jinno K (2002) Miniaturized sample preparation and separation methods for environmental and drug analyses. Anal Sci 18:7–17

    Article  CAS  Google Scholar 

  13. Sobhi HR, Ghambarian M, Behbahani M, Esrafili A (2017) Application of dispersive solid phase extraction based on a surfactant-coated titanium-based nanomagnetic sorbent for preconcentration of bisphenol a in water samples. J Chromatogr A 1518:25–33

    Article  CAS  Google Scholar 

  14. Sobhi HR, Ghambarian M, Esrafili A, Behbahani M (2017) A nanomagnetic and 3-mercaptopropyl-functionalized silica powder for dispersive solid phase extraction of hg (II) prior to its determination by continuous-flow cold vapor AAS. Microchim Acta 184:2317–2323

    Article  CAS  Google Scholar 

  15. Sobhi HR, Mohammadzadeh A, Behbahani M, Esrafili A (2019) Implementation of an ultrasonic assisted dispersive μ-solid phase extraction method for trace analysis of lead in aqueous and urine samples. Microchem J 146:782–788

    Article  CAS  Google Scholar 

  16. Ocaña-González JA, Fernández-Torres R, Bello-López MÁ, Ramos-Payán M (2016) New developments in microextraction techniques in bioanalysis. A review. Anal Chim Acta 905:8–23

    Article  Google Scholar 

  17. Šafařı́ková M, Šafařı́k I (1999) Magnetic solid-phase extraction. J Magn Magn Mater 194:108–112

    Article  Google Scholar 

  18. Jiang R, Pawliszyn J (2012) Thin-film microextraction offers another geometry for solid-phase microextraction. TrAC Trends Anal Chem 39:245–253

    Article  CAS  Google Scholar 

  19. Bordin DCM, Alves MNR, De Campos EG, De Martinis BS (2016) Disposable pipette tips extraction: fundamentals, applications and state of the art. J Sep Sci 39(6):1168–1172

    Article  CAS  Google Scholar 

  20. Shukla AK, Shukla A, Shukla M (2000) Micro-volume spin columns for sample preparation. US Patent 6:103–195

    Google Scholar 

  21. Namera A, Nakamoto A, Nishida M, Saito T, Kishiyama I, Miyazaki S, Yahata M, Yashiki M, Nagao M (2008) Extraction of amphetamines and methylenedioxyamphetamines from urine using a monolithic silica disk-packed spin column and high-performance liquid chromatography–diode array detection. J Chromatogr A 1208:71–75

    Article  CAS  Google Scholar 

  22. Kumazawa T, Hasegawa C, Lee X-P, Sato K (2010) New and unique methods of solid-phase extraction for use before instrumental analysis of xenobiotics in human specimens. Forensic Toxicol 28:61–68

    Article  CAS  Google Scholar 

  23. Xu L, Qi X, Li X, Bai Y, Liu H (2016) Recent advances in applications of nanomaterials for sample preparation. Talanta 146:714–726

    Article  CAS  Google Scholar 

  24. Bagheri A, Taghizadeh M, Behbahani M, Asgharinezhad AA, Salarian M, Dehghani A, Ebrahimzadeh H, Amini MM (2012) Synthesis and characterization of magnetic metal-organic framework (MOF) as a novel sorbent, and its optimization by experimental design methodology for determination of palladium in environmental samples. Talanta 99:132–139

    Article  CAS  Google Scholar 

  25. Salarian M, Ghanbarpour A, Behbahani M, Bagheri S, Bagheri A (2014) A metal-organic framework sustained by a nanosized Ag12 cuboctahedral node for solid-phase extraction of ultra traces of lead (II) ions. Microchim Acta 181:999–1007

    Article  CAS  Google Scholar 

  26. Furukawa H, Cordova KE, O’Keeffe M, Yaghi OM (2013) The chemistry and applications of metal-organic frameworks. Science (341) 6149:1230444

    Article  Google Scholar 

  27. Jauregui O, Moyano E, Galceran MT (1998) Liquid chromatography–atmospheric pressure chemical ionization mass spectrometry for chlorinated phenolic compounds: application to the analysis of polluted soils. J Chromatogr A 823:241–248

    Article  CAS  Google Scholar 

  28. Denysenko D, Grzywa M, Jelic J, Reuter K, Volkmer D (2014) Scorpionate-type coordination in MFU-4l metal–organic frameworks: small-molecule binding and activation upon the thermally activated formation of open metal sites. Angew Chemie Int Ed 53:5832–5836

    Article  CAS  Google Scholar 

  29. Tajik M, Yamini Y, Esrafili A, Ebrahimpour B (2015) On-line extraction and determination of two herbicides: comparison between two modes of three-phase hollow fiber microextraction. J Sep Sci 38:649–655

    Article  CAS  Google Scholar 

  30. Balasubramanian M, Ramakrishnan V, Rajendran S (1991) Vibrational spectra of (NH4)3ZnCl5. Pramana 36:603–610

    Article  CAS  Google Scholar 

  31. Peng J-F, Liu J-F, Hu X-L, Jiang G-B (2007) Direct determination of chlorophenols in environmental water samples by hollow fiber supported ionic liquid membrane extraction coupled with high-performance liquid chromatography. J Chromatogr A 1139:165–170

    Article  CAS  Google Scholar 

  32. Lee M-R, Yeh Y-C, Hsiang W-S, Hwang B-H (1998) Solid-phase microextraction and gas chromatography–mass spectrometry for determining chlorophenols from landfill leaches and soil. J Chromatogr A 806:317–324

    Article  CAS  Google Scholar 

  33. Cai Y, Cai Y, Mou S, Lu Y (2005) Multi-walled carbon nanotubes as a solid-phase extraction adsorbent for the determination of chlorophenols in environmental water samples. J Chromatogr A 1081:245–247

    Article  CAS  Google Scholar 

  34. Fattahi N, Assadi Y, Hosseini MRM, Jahromi EZ (2007) Determination of chlorophenols in water samples using simultaneous dispersive liquid–liquid microextraction and derivatization followed by gas chromatography-electron-capture detection. J Chromatogr A 1157:23–29

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledge the financial support (NO. 97-3-75-13066) of Iran University of Medical Sciences (Tehran, Iran).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Mahnaz Ghambarian.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOCX 83 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Esrafili, A., Ghambarian, M., Tajik, M. et al. Spin-column micro-solid phase extraction of chlorophenols using MFU-4l metal-organic framework. Microchim Acta 187, 39 (2020). https://doi.org/10.1007/s00604-019-4023-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-019-4023-3

Keywords

Navigation