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Hydrophilic deep eutectic solvents modified phenolic resin as tailored adsorbent for the extraction and determination of levofloxacin and ciprofloxacin from milk

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Abstract

A reliable and efficient method for the simultaneous extraction and determination of antibiotics of ciprofloxacin and levofloxacin from milk was developed with solid phase extraction based on tailored adsorbent materials of deep eutectic solvents modified phenolic resin (DES-R-SPE). Six types of polyhydric alcohol-based hydrophilic DESs were prepared to modify the phenolic resin with the compositions of 3-aminophenol as a functional monomer, glyoxylic acid as a crosslinker, and polyethylene glycol 6000 as a porogen. And the prepared DES-Rs showed better extraction capacities for the target analytes than the unmodified phenolic resin because of more hydrogen bonding and electrostatic interactions supplied by DESs. The choline chloride-glycerol–based resin (DES1-R) with the highest adsorption amounts was selected and the adsorption behavior of it was studied with static adsorption and the dynamic adsorption performance; the adsorption process followed Freundlich isotherm (R2 ≥ 0.9337) and pseudo-second-order (R2 ≥ 0.9951). The present DES1-R-SPE method showed good linear range from 0.5 to100 μg mL−1 (R2 ≥ 0.9998), good recoveries of spiked milk samples (LEV, 96.7%; CIP, 101.5%), and satisfied repeatability for intra-day and inter-day (LEV, RSD≤5.4%; CIP, RSD≤4.6%).

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References

  1. Vakh C, Pochivalov A, Koronkiewicz S, Kalinowski S, Postnov V, Bulatov A. A chemiluminescence method for screening of fluoroquinolones in milk samples based on a multi-pumping flow system. Food Chem. 2019;270:10–6.

    Article  CAS  Google Scholar 

  2. Zheng Y, Wang ZQ, Lui G, Hirt D, Treluyer JM, Benaboud S, et al. Simultaneous quantification of levofloxacin, pefloxacin, ciprofloxacin and moxifloxacin in microvolumes of human plasma using high-performance liquid chromatography with ultraviolet detection. Biomed Chromatogr. 2019;33(5):e4506.

  3. Wang YF, Wang YG, Ouyang XK, Yang LY. Surface-imprinted magnetic carboxylated cellulose nanocrystals for the highly selective extraction of six fluoroquinolones from egg samples. ACS Appl Mater Interfaces. 2017;9(2):1759–69.

    Article  CAS  Google Scholar 

  4. Xu J, Li X, Li C, Chen J, Xiao YX. Hexafluoroisopropanol-induced salt-free catanionic surfactant coacervate extraction method for determination of fluoroquinolones in milk samples. Food Chem. 2018;242:122–30.

    Article  CAS  Google Scholar 

  5. Sun KX, Dong SN, Sun YY, Gao B, Du WC, Xu HX, et al. Graphene oxide-facilitated transport of levofloxacin and ciprofloxacin in saturated and unsaturated porous media. J Hazard Mater. 2018;348:92–9.

    Article  CAS  Google Scholar 

  6. Ma W, Row KH. Simultaneous determination of levofloxacin and ciprofloxacin in human urine by ionic-liquid-based, dual-template molecularly imprinted coated graphene oxide monolithic solid-phase extraction. J Sep Sci. 2019;42(3):642–9.

    Article  CAS  Google Scholar 

  7. Zhu YR, Lu YG, Shi LY, Yang YL. beta-Cyclodextrin functionalized N,Zn codoped carbon dots for specific fluorescence detection of fluoroquinolones in milk samples. Microchem J. 2020;153:104517.

  8. Kantiani L, Farre M, Barcelo D. Rapid residue analysis of fluoroquinolones in raw bovine milk by online solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry. J Chromatogr A. 2011;1218(50):9019–27.

    Article  CAS  Google Scholar 

  9. Ye ZW, Huang YF, Luo Q, Wang L, Huang XJ. Preparation of highly fluorinated and boron-rich adsorbent for magnetic solid-phase extraction of fluoroquinolones in water and milk samples. J Chromatogr A. 1601;2019:86–94.

    Google Scholar 

  10. Panda D, Dash BP, Manickam S, Boczkaj G. Recent advancements in LC-MS based analysis of biotoxins: present and future challenges. Mass Spectrom Rev. 2021.

  11. Yu H, Jia YQ, Wu R, Chen XF, Chan TWD. Determination of fluoroquinolones in food samples by magnetic solid-phase extraction based on a magnetic molecular sieve nanocomposite prior to high-performance liquid chromatography and tandem mass spectrometry. Anal Bioanal Chem. 2019;411(13):2817–26.

    Article  CAS  Google Scholar 

  12. Li X, Cui YY, Yang CX, Yan XP. Synthesis of carboxyl functionalized microporous organic network for solid phase extraction coupled with highperformance liquid chromatography for the determination of phenols in water samples. Talanta. 2020;208:120434.

  13. Lian LL, Zhang XY, Hao J, Lv JY, Wang XY, Zhu B, et al. Magnetic solid-phase extraction of fluoroquinolones from water samples using titanium-based metal-organic framework functionalized magnetic microspheres. J Chromatogr A. 2018;1579:1–8.

    Article  CAS  Google Scholar 

  14. Wang MW, Nie HL, Han DD, Qiao XQ, Yan HY, Shen SG. Cauliflower-like resin microspheres with tuneable surface roughness as solid-phase extraction adsorbent for efficient extraction and determination of plant growth regulators in cucumbers. Food Chem. 2019;295:259–66.

    Article  CAS  Google Scholar 

  15. Tang WY, Row KH. Fabrication of water-compatible molecularly imprinted resin in a hydrophilic deep eutectic solvent for the determination and purification of quinolones in wastewaters. Polymers-Basel. 2019;11(5):871.

  16. Xie YZ, Wang MW, Chen X, Wang SF, Han DD, Han YH, et al. 3-aminophenol-glyoxylic acid resin for the determination of triazine herbicides in tomatoes. Anal Chim Acta. 2019;1061:122–33.

    Article  CAS  Google Scholar 

  17. Han YH, Wang ZQ, Jia J, Bai LG, Liu HY, Shen SG, et al. Newly designed molecularly imprinted 3-aminophenol-glyoxal-urea resin as hydrophilic solid-phase extraction sorbent for specific simultaneous determination of three plant growth regulators in green bell peppers. Food Chem. 2020;311:125999.

  18. Wang MW, Liang SR, Bai LG, Qiao FX, Yan HY. Green protocol for the preparation of hydrophilic molecularly imprinted resin in water for the efficient selective extraction and determination of plant hormones from bean sprouts. Anal Chim Acta. 2019;1064:47–55.

    Article  CAS  Google Scholar 

  19. Li PF, Lu YK, Cao JX, Li MY, Yang CL, Yan HY. Imidazolium ionic-liquid-modified phenolic resin for solid-phase extraction of thidiazuron and forchlorfenuron from cucumbers. J Chromatogr A. 2020;1623:461192.

  20. Harifi-Mood AR, Mohammadpour F, Boczkaj G. Solvent dependency of carbon dioxide Henry's constant in aqueous solutions of choline chlorideethylene glycol based deep eutectic solvent. J Mol Liq. 2020;319:114173.

  21. Janicka P, Przyjazny A, Boczkaj G. Novel “acid tuned” deep eutectic solvents based on protonated L-proline. J Mol Liq. 2021;333:115965.

    Article  CAS  Google Scholar 

  22. Haq HU, Balal M, Castro-Muñoz R, Hussain Z, Safi F, Ullah S, et al. Deep eutectic solvents based assay for extraction and determination of zinc in fish and eel samples using FAAS. J Mol Liq. 2021;333:115930.

    Article  CAS  Google Scholar 

  23. Cai CY, Li FF, Liu LL, Tan ZJ. Deep eutectic solvents used as the green media for the efficient extraction of caffeine from Chinese dark tea. Sep Purif Technol. 2019;227:115723.

  24. Li LN, Liu YM, Wang ZT, Yang L, Liu HW. Development and applications of deep eutectic solvent derived functional materials in chromatographic separation. J Sep Sci. 2020;44(6):1098-1121

  25. Fu NJ, Li LT, Liu KJ, Kim CK, Li J, Zhu T, et al. A choline chloride-acrylic acid deep eutectic solvent polymer based on Fe3O4 particles and MoS2 sheets (poly(ChCl-AA DES)@Fe3O4@MoS2) with specific recognition and good antibacterial properties for beta-lactoglobulin in milk. Talanta. 2019;197:567–77.

    Article  CAS  Google Scholar 

  26. Ge X, Gu CD, Wang XL, Tu JP. Deep eutectic solvents (DESs)-derived advanced functional materials for energy and environmental applications: challenges, opportunities, and future vision. J Mater Chem A. 2017;5(18):8209–29.

    Article  CAS  Google Scholar 

  27. Li LN, Liu YM, Wang ZT, Yang L, Liu HW. Development and applications of deep eutectic solvent derived functional materials in chromatographic separation. J Sep Sci. 2020;44(6):1098-1121.

  28. Xue J, Wang J, Feng DS, Huang HF, Wang M. Processing of functional composite resins using deep eutectic solvent. Crystals. 2020;10(10).

  29. Shishov A, Pochivalov A, Nugbienyo L, Andruch V, Bulatov A. Deep eutectic solvents are not only effective extractants. TrAC Trends Anal Chem. 2020;129:115956.

    Article  CAS  Google Scholar 

  30. Tome LIN, Baiao V, da Silva W, Brett CMA. Deep eutectic solvents for the production and application of new materials. Appl Mater Today. 2018;10:30–50.

    Article  Google Scholar 

  31. Deep eutectic solvents based highly efficient extractive desulfurization of fuels-eco-friendly approach. J Mol Liq. 2019;296:111916.

  32. Warrag SEE, Darwish AS, Adeyemi IA, Hadj-Kali MK, Kroon MC, AlNashef IM. Extraction of pyridine from n-alkane mixtures using methyltriphenylphosphonium bromide-based deep eutectic solvents as extractive denitrogenation agents. Fluid Phase Equilib. 2020;517:112622.

  33. Yu H, Wang ZH, Wu R, Chen XF, Chan TWD. Water-dispersible pH/thermo dual-responsive microporous polymeric microspheres as adsorbent for dispersive solid-phase extraction of fluoroquinolones from environmental water samples and food samples. J Chromatogr A. 1601;2019:27–34.

    Google Scholar 

  34. Yu KL, Yue ME, Xu J, Jiang TF. Determination of fluoroquinolones in milk, honey and water samples by salting out-assisted dispersive liquid-liquid microextraction based on deep eutectic solvent combined with MECC. Food Chem. 2020;332:127371.

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Funding

This study was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea Government (MSIT) (No.NRF-2019R1A2C1010032).

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Correspondence to Kyung Ho Row.

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Ma, W., Row, K.H. Hydrophilic deep eutectic solvents modified phenolic resin as tailored adsorbent for the extraction and determination of levofloxacin and ciprofloxacin from milk. Anal Bioanal Chem 413, 4329–4339 (2021). https://doi.org/10.1007/s00216-021-03389-2

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