Analytical and Bioanalytical Chemistry

, Volume 410, Issue 6, pp 1647–1656 | Cite as

Synthesis and application of imidazolium-based ionic liquids as extraction solvent for pretreatment of triazole fungicides in water samples

  • Jiale Yang
  • Chen Fan
  • Dandan Kong
  • Gang Tang
  • Wenbing Zhang
  • Hongqiang Dong
  • You Liang
  • Deng Wang
  • Yongsong Cao
Paper in Forefront


Five novel ionic liquids (ILs), 1,3-dibutylimidazolium bromide [BBMIm][Br], 1-pentyl-3-butylimidazolium bromide [BPMIm][Br], 1-hexyl-3-butylimidazolium bromide [BHMIm][Br], 1,1'-(butane-1,4-diyl)bis(3-butylimidazolium) bromide [C4(BMIm)2][Br2], and 1,1'-(butane-1,4-diyl)bis(3-methylimidazolium) bromide [C4(MIm)2][Br2], were prepared and used in situ to react with bis(trifluoromethane)sulfonamide lithium salt to extract the myclobutanil, tebuconazole, cyproconazole, and prothioconazole from water samples. The results showed that mono-cationic ILs had much better recovery than dicationic ILs, and mono-imidazolium IL bearing butyl groups at N-1 and N-3 sites had the best recovery. When the length of the alkyl substituent group was more than four carbons at N-3 site, the recovery decreased with increase of alkyl chain length of 1-butylimidazolium IL. The extraction efficiency order of triazoles from high to low was [BBMIm][Br], [BPMIm][Br], [BHMIm][Br], [BMIm][Br] (1-butyl-3-methylimidazolium bromide), [C4(BMIm)2]Br2, [C4(MIm)2]Br2. An in situ ionic liquid dispersive liquid–liquid microextraction combined with ultrasmall superparamagnetic Fe3O4 was established as a pretreatment method for enrichment of triazole fungicides in water samples by using the synthetic [BBMIm][Br] as the cationic IL and used to detect analytes followed by high-performance liquid chromatography. Under the optimized conditions, the proposed method showed a good linearity within a range of 5–250 μg L−1, with the determination coefficient (r2) varying from 0.998 to 0.999. High mean enrichment factors were achieved ranging from 187 to 323, and the recoveries of the target analytes from real water samples at spiking levels of 10.0, 20.0, and 50.0 μg L−1 were between 70.1% and 115.0%. The limits of detection for the analytes were 0.74–1.44 μg L−1, and the intra-day relative standard deviations varied from 5.23% to 8.65%. The proposed method can be further applied to analyze and monitor pesticides in other related samples.

Graphical Abstract

The scheme of the in-situ DLLME method for the determination of triazoles using the imidazolium-based ionic liquids


Ionic liquids In situ ionic liquid–dispersive liquid–liquid microextraction Pretreatment Triazole fungicides Ultrasmall superparamagnetic Fe3O4 



The authors acknowledge financial support of this work by the National Key Research and Development Program of China (2016YFF0203802) and the National Natural Science Foundation of China (31672067).

Compliance with ethical Standards

Conflicts of interest

All authors of this article declare no conflict of interest.

Ethical Approval

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

Supplementary material

216_2017_820_MOESM1_ESM.pdf (6.2 mb)
ESM 1 (PDF 455 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  • Jiale Yang
    • 1
  • Chen Fan
    • 1
  • Dandan Kong
    • 1
  • Gang Tang
    • 1
  • Wenbing Zhang
    • 1
  • Hongqiang Dong
    • 1
  • You Liang
    • 1
  • Deng Wang
    • 1
  • Yongsong Cao
    • 1
  1. 1.College of Plant Protection, China Agricultural UniversityBeijingChina

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