Skip to main content
Log in

Evaluation of fatty acid/alcohol-based hydrophobic deep eutectic solvents as media for extracting antibiotics from environmental water

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Fatty acid/alcohol-based hydrophobic deep eutectic solvents (DESs) have been considered to be eco-friendly alternatives to replace conventional hydrophobic organic solvents (i.e., halogenated solvents). These novel eco-friendly solvents are applied in the extraction and determination of two antibiotics (levofloxacin, LOF; ciprofloxacin, COF) in environmental water by liquid–liquid microextraction (LLME). Two different families of hydrophobic DESs, one based on fatty acids and the other on fatty alcohols, were prepared and applied as a microextraction solvent. The study results showed that 1-octanol/ tricaprylylmethylammonium chloride-based DES (DES-14) had the best extraction efficiency. The vortex-assisted method exhibited better extraction efficiency than the heating, ultrasound, and microwave auxiliary methods in LLME. The main factors affecting the vortex-assisted LLME were optimized statistically using the Box-Behnken design (BBD) combined with response surface methodology (RSM). The optimal conditions for LOF and COF were as follows: 14:174 μL DES, 5.7 min vortex-assisted time, and 8.7% NaCl, w/v. Under these conditions, hydrophobic DES-based LLME was established for extraction and determination LOF and COF from environmental water, and the extraction recoveries of LOF and COF exceeded 94.8%. The proposed hydrophobic DES-based LLME method provides high precision, good linearity, acceptable limit of detection (LOD) and limit of quantification (LOQ), and satisfactory recoveries for the targets. These results support the potential of this method as a new type of extraction medium to replace conventional hydrophobic organic solvents in various applications.

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
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Lamei N, Ezoddin M, Ardestani MS, Abdi K. Dispersion of magnetic graphene oxide nanoparticles coated with a deep eutectic solvent using ultrasound assistance for preconcentration of methadone in biological and water samples followed by GC-FID and GC-MS. Anal Bioanal Chem. 2017;409:6113–21.

    Article  CAS  Google Scholar 

  2. Męczykowska H, Kobylis P, Stepnowski P, Caban M. Ionic liquids for the passive sampling of sulfonamides from water—applicability and selectivity study. Anal Bioanal Chem. 2017;409:3951–8.

    Article  Google Scholar 

  3. Yang J, Fan C, Kong D, Tang G, Zhang W, Dong H, et al. Synthesis and application of imidazolium-based ionic liquids as extraction solvent for pretreatment of triazole fungicides in water samples. Anal Bioanal Chem. 2018;410:1647–56.

    Article  CAS  Google Scholar 

  4. Ren JY, Wang XL, Li XL, Wang ML, Zhao RS, Lin JM. Magnetic covalent triazine-based frameworks as magnetic solid-phase extraction adsorbents for sensitive determination of perfluorinated compounds in environmental water samples. Anal Bioanal Chem. 2018;410:1657–65.

    Article  CAS  Google Scholar 

  5. Zhang H, Qiao X, Cai T, Chen J, Li Z, Qiu H. Preparation and characterization of carbon dot-decorated silica stationary phase in deep eutectic solvents for hydrophilic interaction chromatography. Anal Bioanal Chem. 2017;409:2401–10.

    Article  CAS  Google Scholar 

  6. Piovesana S, Capriotti AL, Cavaliere C, La Barbera G, Samperi R, Chiozzi RZ, et al. A new carbon-based magnetic material for the dispersive solid-phase extraction of UV filters from water samples before liquid chromatography–tandem mass spectrometry analysis. Anal Bioanal Chem. 2017;409:4181–94.

    Article  CAS  Google Scholar 

  7. Szultka-Mlynska M, Buszewski B. Erratum to: Study of in-vitro metabolism of selected antibiotic drugs in human liver microsomes by liquid chromatography coupled with tandem mass spectrometry. Anal Bioanal Chem. 2017;409:351–3.

    Article  CAS  Google Scholar 

  8. Li D, Ma X, Wang R, Yu Y. Determination of trace bisphenol A in environmental water by high-performance liquid chromatography using magnetic reduced graphene oxide based solid-phase extraction coupled with dispersive liquid–liquid microextraction. Anal Bioanal Chem. 2017;409:1165–72.

    Article  CAS  Google Scholar 

  9. Borraccetti MD, Damiani PC, Olivieri AC. When unfolding is better: unique success of unfolded partial least-squares regression with residual bilinearization for the processing of spectral-pH data with strong spectral overlapping. Analysis of fluoroquinolones in human urine based on flow-injection pH-modulated synchronous fluorescence data matrices. Analyst. 2009;134:1682–91.

    Article  CAS  Google Scholar 

  10. Li Y, Zhang Z, Li J, Li H, Chen Y, Liu Z. Simple, stable, and sensitive electrogenerated chemiluminescence detector for high-performance liquid chromatography and its application in direct determination of multiple fluoroquinolone residues in milk. Talanta. 2011;84:690–5.

    Article  CAS  Google Scholar 

  11. Yang X, Wang R, Wang W, Yan H, Qiu M, Song Y. Synthesis of a novel molecularly imprinted organic–inorganic hybrid polymer for the selective isolation and determination of fluoroquinolones in tilapia. J Chromatogr B. 2014;945:127–34.

    Article  Google Scholar 

  12. Briars R, Paniwnyk L. Effect of ultrasound on the extraction of artemisinin from Artemisia annua. Ind Crop Prod. 2013;42:595–600.

    Article  CAS  Google Scholar 

  13. Khezeli T, Daneshfar A, Sahraei R. Emulsification liquid–liquid microextraction based on deep eutectic solvent: an extraction method for the determination of benzene, toluene, ethylbenzene, and seven polycyclic aromatic hydrocarbons from water samples. J Chromatogr A. 2015;1425:25–33.

    Article  CAS  Google Scholar 

  14. Gałuszka A, Migaszewski Z, Namieśnik J. The 12 principles of green analytical chemistry and the SIGNIFICANCE mnemonic of green analytical practices. Trac-Trend Anal Chem. 2013;50:78–84.

    Article  Google Scholar 

  15. Lavilla I, Romero V, Costas I, Bendicho C. Greener derivatization in analytical chemistry. Trac-Trend Anal Chem. 2014;61:1–10.

    Article  CAS  Google Scholar 

  16. Pham TPT, Cho CW, Yun YS. Environmental fate and toxicity of ionic liquids: a review. Water Res. 2010;44:352–72.

    Article  CAS  Google Scholar 

  17. Frade RF, Afonso CA. Impact of ionic liquids in environment and humans: an overview. Hum Exp Toxicol. 2010;29:1038–54.

    Article  CAS  Google Scholar 

  18. Smith EL, Abbott AP, Ryder KS. Deep eutectic solvents (DESs) and their applications. Chem Rev. 2014;114:11060–82.

    Article  CAS  Google Scholar 

  19. Tang W, Liu L, Li G, Zhu T, Row KH. Optimal separation of phenol from model oils by forming deep eutectic solvents with quaternary ammonium salts. Korean J Chem Eng. 2017;34:814–21.

    Article  CAS  Google Scholar 

  20. Van Osch DJ, Parmentier D, Dietz CH, van den Bruinhorst A, Tuinier R, Kroon MC. Removal of alkali and transition metal ions from water with hydrophobic deep eutectic solvents. Chem Commun. 2016;52:11987–90.

    Article  Google Scholar 

  21. Espino M, de los Ángeles Fernández M, Gomez FJ, Silva MF. Natural designer solvents for greening analytical chemistry. Trac Trends Anal Chem. 2016;76:126–36.

    Article  CAS  Google Scholar 

  22. Dai Y, Witkamp GJ, Verpoorte R, Choi YH. Natural deep eutectic solvents as new extraction media for phenolic metabolites in Carthamus tinctorius L. Anal Chem. 2013;85:6272–8.

    Article  CAS  Google Scholar 

  23. Passos H, Tavares DJ, Ferreira AM, Freire MG, Coutinho JA. Are aqueous biphasic systems composed of deep eutectic solvents ternary or quaternary systems? ACS Sustain Chem Eng. 2016;4:2881–6.

    Article  CAS  Google Scholar 

  24. Gu T, Zhang M, Tan T, Chen J, Li Z, Zhang Q, et al. Deep eutectic solvents as novel extraction media for phenolic compounds from model oil. Chem Commun. 2014;50:11749–52.

    Article  CAS  Google Scholar 

  25. Yan H, Wang H, Qin X, Liu B, Du J. Ultrasound-assisted dispersive liquid–liquid microextraction for determination of fluoroquinolones in pharmaceutical wastewater. J Pharm Biomed. 2011;54:53–7.

    Article  CAS  Google Scholar 

  26. Tang B, Bi W, Zhang H, Row KH. Deep eutectic solvent-based HS-SME coupled with GC for the analysis of bioactive terpenoids in Chamaecyparis obtusa leaves. Chromatographia. 2014;77:373–7.

    Article  CAS  Google Scholar 

  27. Bi W, Tian M, Row KH. Evaluation of alcohol-based deep eutectic solvent in extraction and determination of flavonoids with response surface methodology optimization. J Chromatogr A. 2013;1285:22–30.

    Article  CAS  Google Scholar 

  28. Qi XL, Peng X, Huang YY, Li L, Wei ZF, Zu YG, et al. Green and efficient extraction of bioactive flavonoids from Equisetum palustre L. by deep eutectic solvents-based negative pressure cavitation method combined with macroporous resin enrichment. Ind Crop Prod. 2015;70:142–8.

    Article  CAS  Google Scholar 

  29. Hayyan M, Mjalli FS, Hashim MA, AlNashef IM. A novel technique for separating glycerine from palm oil-based biodiesel using ionic liquids. Fuel Process Technol. 2010;91:116–20.

    Article  CAS  Google Scholar 

  30. Wang Y, Hou Y, Wu W, Liu D, Ji Y, Ren S. Roles of a hydrogen bond donor and a hydrogen bond acceptor in the extraction of toluene from n-heptane using deep eutectic solvents. Green Chem. 2016;18:3089–97.

    Article  CAS  Google Scholar 

  31. Cao J, Yang M, Cao F, Wang J, Su E. Tailor-made hydrophobic deep eutectic solvents for cleaner extraction of polyprenyl acetates from Ginkgo biloba leaves. J Clean Prod. 2017;152:399–405.

    Article  CAS  Google Scholar 

  32. Abbott AP, Capper G, Davies DL, Rasheed RK, Tambyrajah V. Novel solvent properties of choline chloride/urea mixtures. Chem Commun. 2003;1:70–1.

    Article  Google Scholar 

  33. Guo W, Hou Y, Wu W, Ren S, Tian S, Marsh KN. Separation of phenol from model oils with quaternary ammonium salts via forming deep eutectic solvents. Green Chem. 2013;15:226–9.

    Article  CAS  Google Scholar 

  34. Tang W, Gao F, Duan Y, Zhu T, Row KH. Exploration of deep eutectic solvent-based molecularly imprinted polymers as solid-phase extraction sorbents for screening chloramphenicol in milk. J Chromatogr Sci. 2017;55:654–61.

    Article  CAS  Google Scholar 

  35. Zhu S, Zhou J, Jia H, Zhang H. Liquid–liquid microextraction of synthetic pigments in beverages using a hydrophobic deep eutectic solvent. Food Chem. 2018;243:351–6.

    Article  CAS  Google Scholar 

  36. Tang W, Li G, Chen B, Zhu T, Row KH. Evaluating ternary deep eutectic solvents as novel media for extraction of flavonoids from Ginkgo biloba. Sep Sci Technol. 2017;52:91–9.

    Article  CAS  Google Scholar 

  37. Yilmaz E, Soylak M. Ultrasound assisted-deep eutectic solvent based on emulsification liquid phase microextraction combined with microsample injection flame atomic absorption spectrometry for valence speciation of chromium (III/VI) in environmental samples. Talanta. 2016;160:680–5.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This study was support by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the ministry of education (NRF-2015R1A4A1042434).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Kyung Ho Row.

Ethics declarations

This article does not contain any studies with human participants or animals performed by any of the authors.

The authors declare that they have no competing interests.

Electronic supplementary material

ESM 1

(PDF 2649 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tang, W., Dai, Y. & Row, K.H. Evaluation of fatty acid/alcohol-based hydrophobic deep eutectic solvents as media for extracting antibiotics from environmental water. Anal Bioanal Chem 410, 7325–7336 (2018). https://doi.org/10.1007/s00216-018-1346-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1346-6

Keywords

Navigation