Analytical and Bioanalytical Chemistry

, Volume 410, Issue 25, pp 6619–6632 | Cite as

Development and application of metal organic framework/chitosan foams based on ultrasound-assisted solid-phase extraction coupling to UPLC-MS/MS for the determination of five parabens in water

  • Shuo Li
  • Mengtian Jia
  • Hongqiao Guo
  • Xiaohong HouEmail author
Research Paper


In this work, a variety of highly porous metal organic framework/chitosan (MOF/CS) foams (MIL-53(Al)/CS, MIL-53(Fe)/CS, MIL-101(Cr)/CS, MIL-101(Fe)/CS, UiO-66(Zr)/CS, and MIL-100(Fe)/CS) were designed and prepared by an ice-templating process. The introduction of MOFs made these foams achieve excellent inherent characters in terms of strength, stability, and adsorption ability. The MOFs incorporated in the foams retained their unique properties. Additionally, the foams were durable and their adsorption abilities had only a little loss after being recycled several times. MIL-53(Al)/CS foam was selected as an adsorbent candidate to develop an ultrasound-assisted solid-phase extraction (UA-SPE) method for the first time, owing to its particularly noteworthy performance among the prepared MOF/CS foams. The method was then successfully applied to extract trace amount of five parabens (methylparaben, ethylparaben, propylparaben, butylparaben, benzylparaben) in water samples, followed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) detection. Several experimental parameters were investigated. Under the optimal conditions, the linear ranges were 0.5–200 μg/L with regression coefficients (r2) from 0.9948 to 0.9983. The method detection limits were between 0.09 and 0.45 μg/L. The recoveries ranged from 78.75 to 102.1% with relative standard deviations (RSDs) < 7.4%. Furthermore, the molecular interactions and free binding energies between MOFs and parabens were calculated by means of molecular docking to explain the adsorption mechanism deeply. The novel method proposed in this work exhibited many benefits such as easy operation, high enrichment efficiency, less solvent consuming, and higher sensitivity. Such a strategy would expand the application prospect of MOFs in sample pretreatment.

Graphical abstract


Metal organic framework/chitosan foams Ultrasound-assisted solid-phase extraction Parabens Water samples 


Funding information

The work was financially supported by the Fund for the Natural Science Foundation of Liaoning Province of China (No: 201602693), the Natural Science Foundation of Liaoning Provincial Department of Education of China (No: 2017LQN12), the Training Program Foundation for the Distinguished Young Scholars of University in Liaoning Province (LJQ2015109), and the Virtual Educational Center of Medicinal Chemistry in Liaoning Province.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2018_1269_MOESM1_ESM.pdf (902 kb)
ESM 1 (PDF 902 kb)


  1. 1.
    Yang XC, Xu Q. Bimetallic metal-organic frameworks (MOFs) for gas storage and separation. Cryst Growth Des. 2017;17(4):1450–5.CrossRefGoogle Scholar
  2. 2.
    Kayal S, Sun B, Chakraborty A. Study of metal-organic framework MIL-101(Cr) for natural gas (methane) storage and compare with other MOFs (metal-organic frameworks). Energy. 2015;91:772–81.CrossRefGoogle Scholar
  3. 3.
    Kuang X, Ma Y, Su H, Zhang J, Dong YB, Tang B. High-performance liquid chromatographic enantioseparation of racemic drugs based on homochiral metal-organic framework. Anal Chem. 2014;86(2):1277–81.CrossRefPubMedGoogle Scholar
  4. 4.
    Yang CX, Yan XP. Metal-organic framework MIL-101(Cr) for high-performance liquid chromatographic separation of substituted aromatics. Anal Chem. 2011;83(18):7144–50.CrossRefPubMedGoogle Scholar
  5. 5.
    Subudhi S, Rath D, Parida KM. A mechanistic approach towards the photocatalytic organic transformations over functionalised metal organic frameworks: a review. Catal Sci Technol. 2018;8(3):679–96.CrossRefGoogle Scholar
  6. 6.
    Pu MJ, Guan ZY, Ma YW, Wan J, Wang Y, Brusseau ML, et al. Synthesis of iron-based metal-organic framework MIL-53 as an efficient catalyst to activate persulfate for the degradation of Orange G in aqueous solution. Appl Catal A Gen. 2018;549:82–92.CrossRefPubMedGoogle Scholar
  7. 7.
    Singco B, Liu LH, Chen YT, Shih YH, Huang HY, Lin CH. Approaches to drug delivery: confinement of aspirin in MIL-100(Fe) and aspirin in the de novo synthesis of metal–organic frameworks. Micropor Mesopor Mat. 2016;223:254–60.CrossRefGoogle Scholar
  8. 8.
    Lu N, Wang T, Zhao P, Zhang LJ, Lun XW, Zhang XL, et al. Experimental and molecular docking investigation on metal-organic framework MIL-101(Cr) as a sorbent for vortex assisted dispersive micro-solid-phase extraction of trace 5-nitroimidazole residues in environmental water samples prior to UPLC-MS/MS analysis. Anal Bioanal Chem. 2016;408(29):8515–28.CrossRefPubMedGoogle Scholar
  9. 9.
    Rocío-Bautista P, González-Hernández P, Pino V, Pasán J, Afonso AM. Metal-organic frameworks as novel sorbents in dispersive-based microextraction approaches. Trac Trend Anal Chem. 2017;90:114–34.CrossRefGoogle Scholar
  10. 10.
    Liu SQ, Xie LJ, Hu QK, Yang HS, Pan GR, Zhu F, et al. A tri-metal centered metal-organic framework for solid-phase microextraction of environmental contaminants with enhanced extraction efficiency. Anal Chim Acta. 2017;987:38–46.CrossRefPubMedGoogle Scholar
  11. 11.
    Zhai YJ, Li N, Lei L, Yang X, Zhang H. Dispersive micro-solid-phase extraction of hormones in liquid cosmetics with metal-organic framework. Anal Methods UK. 2014;6(23):9435–45.CrossRefGoogle Scholar
  12. 12.
    Huang W, Jiang J, Wu D, Xu J, Xue B, Kirillov AM. A highly stable nanotubular MOF rotator for selective adsorption of benzene and separation of xylene isomers. Inorg Chem. 2015;54(22):10524–6.CrossRefPubMedGoogle Scholar
  13. 13.
    Chen XF, Zang H, Wang X, Cheng JG, Zhao RS, Cheng CG, et al. Metal-organic framework MIL-53(Al) as a solid-phase microextraction adsorbent for the determination of 16 polycyclic aromatic hydrocarbons in water samples by gas chromatography-tandem mass spectrometry. Analyst. 2012;137(22):5411–9.CrossRefPubMedGoogle Scholar
  14. 14.
    Sajid M. Porous membrane protected micro-solid-phase extraction: a review of features, advancements and applications. Anal Chim Acta. 2017;965:36–53.CrossRefPubMedGoogle Scholar
  15. 15.
    Frizzarin RM, Palomino CC, Bauzà MM, Portugal LA, Maya F, Cerdà V, et al. Submicrometric magnetic nanoporous carbons derived from metal-organic frameworks enabling automated electromagnet-assisted online solid-phase extraction. Anal Chem. 2016;88(14):6990–5.CrossRefPubMedGoogle Scholar
  16. 16.
    Wang T, Zhao P, Lu N, Chen HC, Zhang CL, Hou XH. Facile fabrication of Fe3O4/MIL-101(Cr) for effective removal of acid red 1 and orange G from aqueous solution. Chem Eng J. 2016;295:403–13.CrossRefGoogle Scholar
  17. 17.
    Dai XP, Jia XN, Zhao P, Wang T, Wang J, Huang PT, et al. A combined experimental/computational study on metal-organic framework MIL-101(Cr) as a SPE sorbent for the determination of sulphonamides in environmental water samples coupling with UPLC-MS/MS. Talanta. 2016;154:581–8.CrossRefPubMedGoogle Scholar
  18. 18.
    Kitao T, Zhang YY, Kitagawa S, Wang B, Uemura T. Hybridization of MOFs and polymers. Chem Soc Rev. 2017;46(11):3108–33.CrossRefPubMedGoogle Scholar
  19. 19.
    Hong WY, Perera SP, Burrows AD. Manufacturing of metal-organic framework monoliths and their application in CO2 adsorption. Micropor Mesopor Mat. 2015;214:149–55.CrossRefGoogle Scholar
  20. 20.
    Thakkar H, Eastman S, Al-Naddaf Q, Rownaghi AA, Rezaei F. 3D-printed metal-organic framework monoliths for gas adsorption processes. Acs Appl Mater Inter. 2017;9(41):35908–16.CrossRefGoogle Scholar
  21. 21.
    Ruan HM, Guo CM, Yu HW, Shen JN, Gao CN, Sotto A, et al. Fabrication of a MIL-53(Al) nanocomposite membrane and potential application in desalination of dye solutions. Ind Eng Chem Res. 2016;55(46):12099–110.CrossRefGoogle Scholar
  22. 22.
    Basu S, Balakrishnan M. Polyamide thin film composite membranes containing ZIF-8 for the separation of pharmaceutical compounds from aqueous streams. Sep Purif Technol. 2017;179:118–25.CrossRefGoogle Scholar
  23. 23.
    Chen YF, Huang XQ, Zhang SH, Li SQ, Cao SJ, Pei XK, et al. Shaping of metal-organic frameworks: from fluid to shaped bodies and robust foams. J Am Chem Soc. 2016;138(34):10810–3.CrossRefPubMedGoogle Scholar
  24. 24.
    Zhang NN, Qiu HX, Si YM, Wang W, Gao JP. Fabrication of highly porous biodegradable monoliths strengthened by graphene oxide and their adsorption of metal ions. Carbon. 2011;49(3):827–37.CrossRefGoogle Scholar
  25. 25.
    Fu QS, Wen L, Zhang L, Chen XS, Pun D, Ahmed A, et al. Preparation of ice-templated MOF–polymer composite monoliths and their application for wastewater treatment with high capacity and easy recycling. Acs Appl Mater Inter. 2017;9(39):33979–88.CrossRefGoogle Scholar
  26. 26.
    Jóźwiak T, Filipkowska U, Szymczyk P, Rodziewicz J, Mielcarek A. Effect of ionic and covalent crosslinking agents on properties of chitosan beads and sorption effectiveness of Reactive Black 5 dye. React Funct Polym. 2017;114:58–74.CrossRefGoogle Scholar
  27. 27.
    Liao CY, Liu F, Kannan K. Occurrence of and dietary exposure to parabens in foodstuffs from the United States. Environ Sci Technol. 2013;47(8):3918–25.CrossRefPubMedGoogle Scholar
  28. 28.
    Giulivo M, Lopez dAM, Capri E, Barceló D. Human exposure to endocrine disrupting compounds: their role in reproductive systems, metabolic syndrome and breast cancer. A review. Environ Res. 2016;151:251–64.CrossRefPubMedGoogle Scholar
  29. 29.
    Darbre PD, Harvey PW. Paraben esters: review of recent studies of endocrine toxicity, absorption, esterase and human exposure, and discussion of potential human health risks. J Appl Toxicol. 2010;28(5):561–78.CrossRefGoogle Scholar
  30. 30.
    Julie B, Camilla T, Sofie C, Ulla H. Possible endocrine disrupting effects of parabens and their metabolites. Reprod Toxicol. 2010;30(2):301–12.CrossRefGoogle Scholar
  31. 31.
    Darbre PD, Harvey PW. Parabens can enable hallmarks and characteristics of cancer in human breast epithelial cells: a review of the literature with reference to new exposure data and regulatory status. J Appl Toxicol. 2014;34(9):925–38.CrossRefPubMedGoogle Scholar
  32. 32.
    Becerra-Herrera M, Miranda V, Arismendi D, Richter P. Chemometric optimization of the extraction and derivatization of parabens for their determination in water samples by rotating-disk sorptive extraction and gas chromatography mass spectrometry. Talanta. 2018;176(6):551–7.CrossRefPubMedGoogle Scholar
  33. 33.
    Shen X, Liang J, Zheng LX, Lv QZ, Wang H. Application of dispersive liquid-liquid microextraction for the preconcentration of eight parabens in real samples and their determination by high-performance liquid chromatography. J Sep Sci. 2017;40(22):4385–93.CrossRefPubMedGoogle Scholar
  34. 34.
    Rocío-Bautista P, Martínez-Benito C, Pino V, Pasán J, Ayala JH, Ruiz-Pérez C, et al. The metal-organic framework HKUST-1 as efficient sorbent in a vortex-assisted dispersive micro solid-phase extraction of parabens from environmental waters, cosmetic creams, and human urine. Talanta. 2015;139:13–20.CrossRefPubMedGoogle Scholar
  35. 35.
    Millange F, Guillou N, Medina ME, Férey G, Carlinsinclair A, Golden KM, et al. Selective sorption of organic molecules by the flexible porous hybrid metal−organic framework MIL-53(Fe) controlled by various host−guest interactions. Chem Mater. 2010;22(14):4237–45.CrossRefGoogle Scholar
  36. 36.
    Wang JQ, Chen DM, Li B, Jiao H, Duan DL, Shao DD, et al. Fe-MIL-101 exhibits selective cytotoxicity and inhibition of angiogenesis in ovarian cancer cells via downregulation of MMP. Sci Rep UK. 2016;6:26126.CrossRefGoogle Scholar
  37. 37.
    Gao GH, Li S, Li SJ, Zhao L, Wang T, Hou XH. 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. 2018;1023:35–43.CrossRefPubMedGoogle Scholar
  38. 38.
    Wang T, Wang J, Zhang CL, Yang Z, Dai XP, Cheng MS, et al. Metal-organic framework MIL-101(Cr) as a sorbent of porous membrane-protected micro-solid-phase extraction for the analysis of six phthalate esters from drinking water: a combination of experimental and computational study. Analyst. 2015;140(15):5308–16.CrossRefPubMedGoogle Scholar
  39. 39.
    Gao GH, Li SJ, Li S, Wang YD, Zhao P, Zhang XY, et al. A combination of computational-experimental study on metal-organic frameworks MIL-53(Al) as sorbent for simultaneous determination of estrogens and glucocorticoids in water and urine samples by dispersive micro-solid-phase extraction coupled to UPLC-MS/MS. Talanta. 2018;180:358–67.CrossRefPubMedGoogle Scholar
  40. 40.
    Fotouhi M, Seidi S, Shanehsaz M, Naseri MT. Magnetically assisted matrix solid phase dispersion for extraction of parabens from breast milks. J Chromatogr A. 2017;1504:17–26.CrossRefPubMedGoogle Scholar
  41. 41.
    Yin QH, Zhu YQ, Yang YL. Dispersive liquid–liquid microextraction followed by magnetic solid-phase extraction for determination of four parabens in beverage samples by ultra-performance liquid chromatography tandem mass spectrometry. Food Anal Method. 2018;11(3):797–807.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of PharmacyShenyang Pharmaceutical UniversityShenyangChina
  2. 2.School of Pharmaceutical EngineeringShenyang Pharmaceutical UniversityShenyangChina

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