Microchimica Acta

, 187:124 | Cite as

Acid-base-governed deep eutectic solvent-based microextraction combined with magnetic solid-phase extraction for determination of phenolic compounds

  • Dezhi Yang
  • Yingdong Wang
  • Hong Li
  • Yaling YangEmail author
Original Paper


A sensitive method based on the use of green deep eutectic solvents (DESs) was designed for the determination of bisphenol-A, bisphenol-AF, tetrabromobisphenol-A and 4-tert.-octylphenol followed by HPLC. This method takes advantage of magnetic solid-phase extraction purification and acid-base induced DES liquid-liquid microextraction. The Mg(II)-Al(III) layered double hydroxide-coated magnetic nanoparticles were selected to purify samples. The DESs were systematically prepared by a range of medium-chain saturated fatty acids (C8-C12) and D,L-menthol. The melting point and the extraction efficiency of phenolic compounds were adjusted by changing the carbon chain length of fatty acid in suitable proportions. Acid-base induction significantly improves the extraction efficiency. The method has lower limits of detection ranging from 6 to 11 ng L−1, good linearity (0.05–500 μg L−1) and high enrichment factors (86–91). The method was successfully applied for the determination of four phenolic compounds in beverage samples. The recoveries ranged from 84.4 to 101.3%.

Graphical abstract

Schematic representation of the extraction of four phenolic compounds by medium chain (C8-C12) fatty acid-based eutectic solvent (DES) through acid-base-induction.


Acid-base induction Menthol Fatty acids Green solvents Magnetic nanoparticles Mg(II)-Al(III) layered double hydroxide 



This work was greatly supported by the Analysis and Testing Foundation of Kunming University of Science and Technology (2016 M20152118089 and 2019P20173118001). Yang Dezhi gratefully acknowledges financial support from the 2018 and 2019 Kunming University of Science and Technology Graduate Research, and International Exchange Project Fund and Yunnan Province Ph.D. Academic Newcomer Fund.

Compliance with ethical standards

Conflict of interest

There is no conflict of interest about this article.

Declaration of interests

The authors declare that they do not have competing financial interests or personal relationships that may influence the work reported in this paper.

Supplementary material

604_2020_4109_MOESM1_ESM.docx (4.1 mb)
ESM 1 (DOCX 4.6 mb)


  1. 1.
    Florindo C, Romero L, Rintoul I, Branco LC, Marrucho IM (2018) From phase change materials to green solvents: hydrophobic low viscous fatty acid–based deep eutectic solvents. ACS Sustain Chem Eng 6:3888–3895CrossRefGoogle Scholar
  2. 2.
    Kudłak B, Owczarek K, Namieśnik J (2015) Selected issues related to the toxicity of ionic liquids and deep eutectic solvents—a review. Environ Sci Pollut Res 22:11975–11992CrossRefGoogle Scholar
  3. 3.
    Zdanowicz M, Wilpiszewska K, Spychaj T (2018) Deep eutectic solvents for polysaccharides processing a review. Carbohydr Polym 200:361–380PubMedCrossRefPubMedCentralGoogle Scholar
  4. 4.
    Abbott AP, Capper G, Davies, Rasheed RK, Tambyrajah V (2003) Novel solvent properties of choline chloride/urea mixtures. Chem Commun 0: 70–71Google Scholar
  5. 5.
    Xu K, Wang Y, Wei X, Chen J, Xu P, Zhou Y (2008) Preparation of magnetic molecularly imprinted polymers based on a deep eutectic solvent as the functional monomer for specific recognition of lysozyme. Microchim Acta 185:146CrossRefGoogle Scholar
  6. 6.
    Xu K, Wang Y, Zhang H, Yang Q, Wei X, Xu P, Zhou Y (2017) Solid-phase extraction of DNA by using a composite prepared from multiwalled carbon nanotubes, chitosan, Fe3O4 and a poly(ethylene glycol)-based deep eutectic solvent. Microchim Acta 184:4133–4140CrossRefGoogle Scholar
  7. 7.
    Ribeiro BD, Florindo C, Iff LC, Coelho MA, Marrucho IM (2015) Menthol-based eutectic mixtures: hydrophobic low viscosity solvents. ACS Sustain Chem Eng 3:2469–2477CrossRefGoogle Scholar
  8. 8.
    Smith EL, Abbott AP, Ryder KS (2014) Deep eutectic solvents (DESs) and their applications. Chem Rev 114:11060–11082PubMedCrossRefPubMedCentralGoogle Scholar
  9. 9.
    Abo-Hamad A, Hayyan M, AlSaadi MA, Hashim MA (2015) Potential applications of deep eutectic solvents in nanotechnology. Chem Eng J 273:551–567CrossRefGoogle Scholar
  10. 10.
    Huang Y, Feng F, Jiang J, Qiao Y, Wu T, Voglmeir J, Chen ZG (2017) Green and efficient extraction of rutin from tartary buckwheat hull by using natural deep eutectic solvents. Food Chem 221:1400–1405PubMedCrossRefPubMedCentralGoogle Scholar
  11. 11.
    Verma R, Mohan M, Goud VV, Banerjee T (2018) Operational strategies and comprehensive evaluation of menthol based deep eutectic solvent for the extraction of lower alcohols from aqueous media. ACS Sustain Chem Eng 6:16920–16932CrossRefGoogle Scholar
  12. 12.
    van Osch DJ, Zubeir LF, van den Bruinhorst A, Rocha MA, Kroon MC (2015) Hydrophobic deep eutectic solvents as water-immiscible extractants. Green Chem 17:4518–4521CrossRefGoogle Scholar
  13. 13.
    Florindo C, Branco LC, Marrucho IM (2017) Development of hydrophobic deep eutectic solvents for extraction of pesticides from aqueous environments. Fluid Phase Equilib 448:135–142CrossRefGoogle Scholar
  14. 14.
    Li X, Row KH (2016) Development of deep eutectic solvents applied in extraction and separation. J Sep Sci 39:3505–3520PubMedCrossRefPubMedCentralGoogle Scholar
  15. 15.
    Křížek T, BursováM HR, Kuchař M, Tůma P, Čabala R, Hložek T (2018) Menthol-based hydrophobic deep eutectic solvents: towards greener and efficient extraction of phytocannabinoids. J Clean Prod 193:391–396CrossRefGoogle Scholar
  16. 16.
    Fan C, Gao X, Han T, Pei H, Hu G, Wang W, Qian C (2019) Selective microextraction of polycyclic aromatic hydrocarbons using a hydrophobic deep eutectic solvent composed with an iron oxide-based nanoferrofluid. Microchim Acta 186:560CrossRefGoogle Scholar
  17. 17.
    Karimi M, Shabani AMH, Dadfarnia S (2016) Deep eutectic solvent-mediated extraction for ligand-less preconcentration of lead and cadmium from environmental samples using magnetic nanoparticles. Microchim Acta 183:563–571CrossRefGoogle Scholar
  18. 18.
    Wang R, Sun D, Wang C, Liu L, Li F, Tan Z (2019) Biphasic recognition chiral extraction of threonine enantiomers in a two-phase system formed by hydrophobic and hydrophilic deep-eutectic solvents. Sep Purif Technol 215:102–107CrossRefGoogle Scholar
  19. 19.
    Zhao BY, Xu P, Yang FX, Wu H, Zong MH, Lou WY (2015) Biocompatible deep eutectic solvents based on choline chloride: characterization and application to the extraction of rutin from Sophora japonica. ACS Sustain Chem Eng 3:2746–2755CrossRefGoogle Scholar
  20. 20.
    Ji L, Han Z, Zou Y, Bo Y (2015) Efficient extraction of major catechins in Camellia sinensis leaves using green choline chloride-based deep eutectic solvents. RSC Adv 5:93937–93944CrossRefGoogle Scholar
  21. 21.
    Matong JM, Nyaba L, Nomngongo PN (2017) Determination of As, Cr, Mo, Sb, Se and V in agricultural soil samples by inductively coupled plasma optical emission spectrometry after simple and rapid solvent extraction using choline chloride-oxalic acid deep eutectic solvent. Ecotoxicol Environ Saf 135:152–157PubMedCrossRefPubMedCentralGoogle Scholar
  22. 22.
    Aydin F, Yilmaz E, Soylak M (2018) Vortex assisted deep eutectic solvent (DES)-emulsification liquid-liquid microextraction of trace curcumin in food and herbal tea samples. Food Chem 243:442–447PubMedCrossRefPubMedCentralGoogle Scholar
  23. 23.
    Shishov A, Volodina N, Nechaeva D, Gagarinova S, Bulatov A (2018) Deep eutectic solvents as a new kind of dispersive solvent for dispersive liquid-liquid microextraction. RSC Adv 8:38146–38149CrossRefGoogle Scholar
  24. 24.
    Ren S, Li Q, Li Y, Li S, Han T, Wang J, Peng Y, Bai Y, Ning B, Gao Z (2019) Upconversion fluorescent aptasensor for bisphenol A and 17β-estradiol based on a nanohybrid composed of black phosphorus and gold, and making use of signal amplification via DNA tetrahedrons. Microchim Acta 186:151CrossRefGoogle Scholar
  25. 25.
    Zhou Y, Chen M, Zhao F, Mu D, Zhang Z, Hu J (2015) Ubiquitous occurrence of chlorinated byproducts of bisphenol A and nonylphenol in bleached food contacting papers and their implications for human exposure. Environ Sci Technol 49:7218–7226PubMedCrossRefPubMedCentralGoogle Scholar
  26. 26.
    Yang D, Li X, Meng D, Wang M, Yang Y (2017) Supramolecular solvents combined with layered double hydroxide-coated magnetic nanoparticles for extraction of bisphenols and 4-tert-octylphenol from fruit juices. Food Chem 237:870–876PubMedCrossRefPubMedCentralGoogle Scholar
  27. 27.
    Yang D, Wang Y, Peng J, Xun C, Yang Y (2019) A green deep eutectic solvents microextraction coupled with acid-base induction for extraction of trace phenolic compounds in large volume water samples. Ecotoxicol Environ Saf 178:130–136PubMedCrossRefPubMedCentralGoogle Scholar
  28. 28.
    Ruesgas-Ramón M, Figueroa-Espinoza MC, Durand E (2017) Application of deep eutectic solvents (DES) for phenolic compounds extraction: overview, challenges, and opportunities. J Agric Food Chem 65(18):3591–3601PubMedCrossRefPubMedCentralGoogle Scholar
  29. 29.
    Deng X, Guo Q, Chen X, Xue T, Wang H, Yao P (2014) Rapid and effective sample clean-up based on magnetic multiwalled carbon nanotubes for the determination of pesticide residues in tea by gas chromatography–mass spectrometry. Food Chem 145:853–858PubMedCrossRefPubMedCentralGoogle Scholar
  30. 30.
    Adiguzel G, Sonmez Z, Adiguzel A, Nadaroglu H (2016) Purification and characterization of a thermostable endo-beta-1, 4 mannanase from Weissellaviridescens LB37 and its application in fruit juice clarification. Eur Food Res Technol 242:769–776CrossRefGoogle Scholar
  31. 31.
    Yao W, Wang X, Liang Y, Yu S, Gu P, Sun Y, Xu C, Chen J, Hayat T, Alsaedi A (2018) Synthesis of novel flower-like layered double oxides/carbon dots nanocomposites for U (VI) and 241Am (III) efficient removal: batch and EXAFS studies. Chem Eng J 332:775–786CrossRefGoogle Scholar
  32. 32.
    Daud M, Kamal MS, Shehzad F, Al-Harthi MA (2016) Graphene/layered double hydroxides nanocomposites: a review of recent progress in synthesis and applications. Carbon 104:241–252CrossRefGoogle Scholar
  33. 33.
    Saraji M, Ghani M (2014) Dissolvable layered double hydroxide coated magnetic nanoparticles for extraction followed by high performance liquid chromatography for the determination of phenolic acids in fruit juices. J Chromatogr A 1366:24–30PubMedCrossRefPubMedCentralGoogle Scholar
  34. 34.
    Ferri A, Kumari N, Peila R, Barresi AA (2017) Production of menthol-loaded nanoparticles by solvent displacement. Can J Chem Eng 95:1690–1706CrossRefGoogle Scholar
  35. 35.
    Yang D, Li G, Wu L, Yang Y (2018) Ferrofluid-based liquid-phase microextraction: analysis of four phenolic compounds in milks and fruit juices. Food Chem 261:96–102PubMedCrossRefPubMedCentralGoogle Scholar
  36. 36.
    Shih HK, Shu TY, Ponnusamy VK, Jen JF (2015) A novel fatty-acid-based in-tube dispersive liquid-liquid microextraction technique for the rapid determination of nonylphenol and 4-tert-octylphenol in aqueous samples using high-performance liquid chromatography-ultraviolet detection. Anal Chim Acta 854:70–77PubMedCrossRefPubMedCentralGoogle Scholar
  37. 37.
    Geens T, Apelbaum TZ, Goeyens L, Neels H, Covaci A (2010) Intake of bisphenol A from canned beverages and foods on the Belgian market. Food Addit Contam Part A 27:1627–1637CrossRefGoogle Scholar
  38. 38.
    Cao XL, Corriveau J, Popovic S (2009) Levels of bisphenol A in canned soft drink products in Canadian markets. J Agric Food Chem 57(4):1307–1311PubMedCrossRefPubMedCentralGoogle Scholar
  39. 39.
    Reyes-Gallardo EM, Lucena R, Cárdenas S, Valcárcel M (2016) Dispersive micro-solid phase extraction of bisphenol A from milk using magnetic nylon 6 composite and its final determination by HPLC-UV. Microchem J 124:751–756CrossRefGoogle Scholar
  40. 40.
    Noori L, Ghanemi K (2019) Selective extraction of bisphenol A and 4-nonylphenol from canned tuna and marine fish tissues using choline-based deep eutectic solvents. Chem Pap 73:301–308CrossRefGoogle Scholar
  41. 41.
    Mesa R, Kabir A, Samanidou V, Furton KG (2018) Simultaneous determination of selected estrogenic endocrine disrupting chemicals and bisphenol A residues in whole milk using fabric phase sorptive extraction coupled to HPLC-UV detection and LC-MS/MS. J Sep Sci 42:598–608PubMedCrossRefPubMedCentralGoogle Scholar
  42. 42.
    Wang L, Zhang Z, Zhang J, Zhang L (2016) Magnetic solid-phase extraction using nanoporous three dimensional graphene hybrid materials for high-capacity enrichment and simultaneous detection of nine bisphenol analogs from water sample. J Chromatogr A 1463:1–10PubMedCrossRefPubMedCentralGoogle Scholar
  43. 43.
    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 1518:25–33PubMedCrossRefPubMedCentralGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Faculty of Life Science and TechnologyKunming University of Science and TechnologyKunmingChina
  2. 2.Faculty of Environmental Science and EngineeringKunming University of Science and TechnologyKunmingChina
  3. 3.College of Basic Medical SciencesShenyang Medical CollegeShenyangChina
  4. 4.Research Institute of Product ProcessingYunnan Academy of Agricultural SciencesKunmingChina

Personalised recommendations