Deep Eutectic Solvent Functionalized Graphene Oxide Based Ferrofluid for the Liquid Phase Microextraction of Fluoroquinolones from Water Samples

Abstract:

The development of smart materials have a significant impact on sample preparation and preconcentration methods. Ferrofluid or magnetic fluids (FF) are smart colloidal suspensions of single domain magnetic nanoparticles in a polar or non-polar liquid carrier. In this study, graphene oxide magnetite (GO@Fe₃O₄) and deep eutectic solvent-based choline chloride and ethylene glycol as a carrier liquid were utilized to form GO@Fe₃O₄-DES FF. The synthesised GO@Fe₃O₄-DES FF was characterized using FTIR, SEM, TEM and vibrating sample magnetometer (VSM). GO@Fe₃O₄-DES FF was further developed for the application of GO@Fe₃O₄-DES FF-liquid phase microextraction (LPME) for enrofloxacin as test compound. Several parameters such as type of FF composition and volume, extraction time, desorption solvent volume, desorption time and solution pH were optimised and analysed using HPLC-UV. Under optimum conditions, the developed GO@Fe₃O₄-DES FF-LPME method showed good linearity, R² ≥ 0.9921, repeatability, RSD 0.57 – 9.40 %. The developed GO@Fe₃O₄-DES FF-LPME method was applied for the determination of enrofloxacin in water samples from Langat River Basin, Selangor and the recovery of 71.6 – 112.3% was obtained. In conclusion, the developed GO@Fe₃O₄-DES FF-LPME method for the determination of enrofloxacin showed excellent sensitivity and precision and may be an excellent alternative method for the extraction on water samples.

• Periodical: Key Engineering Materials (Volume 920)
• Pages: 114-121
• DOI: https://doi.org/10.4028/p-fx1521
• Online since: May 2022
• Authors: Rania Edrees Adam Mohammad, Abdalla Ahmed Elbashir, Jamilah Karim, Noorfatimah Yahaya, Nurul Yani Rahim, Mazidatulakmam Miskam*
• Keywords: Deep Eutectic Solvent Based Ferrofluid, Fluoroquinolone, Liquid Phase Microextraction, Magnetic Graphene-Oxide

References

[1] I. Gehrke, A. Geiser, A. Somborn-Schulz, Innovations in nanotechnology for water treatment, Nanotechnol., Sci. Appl. 8 (2015) 1–17.

DOI: 10.2147/nsa.s43773

[2] J. Krogh, S. Lyons, C.J. Lowe, Pharmaceuticals and personal care products in municipal wastewater and the marine receiving environment near Victoria Canada, Front. Mar. Sci. 4 (2017) 415.

DOI: 10.3389/fmars.2017.00415

[3] C.G. Daughton, Pharmaceuticals and the Environment (PiE): Evolution and impact of the published literature revealed by bibliometric analysis, Sci. Total Environ. 562 (2016) 391–426.

DOI: 10.1016/j.scitotenv.2016.03.109

[4] N. Li, T. Zhang, G. Chen, J. Xu, G. Ouyang, F. Zhu, Recent advances in sample preparation techniques for quantitative detection of pharmaceuticals in biological samples, TrAC, Trends Anal. Chem. 142 (2021) 116318.

DOI: 10.1016/j.trac.2021.116318

[5] M.D. Farahani, F. Shemirani, Ferrofluid based dispersive-solid phase extraction for spectrophotometric determination of dyes, J. Colloid Interface Sci. 407 (2013) 250–254.

DOI: 10.1016/j.jcis.2013.05.035

[6] D. Yang, G. Li, L. Wu, Y. Yang, Ferrofluid-based liquid-phase microextraction: Analysis of four phenolic compounds in milks and fruit juices, Food Chem. 261 (2018) 96–102.

DOI: 10.1016/j.foodchem.2018.04.038

[7] A.K. El-Deen, K. Shimizu, Application of D-limonene as a bio-based solvent in low density-dispersive liquid–liquid microextraction of acidic drugs from aqueous samples, Anal. Sci. 35 (2019) 1385–1391.

DOI: 10.2116/analsci.19p360

[8] P. Zohrabi, M. Shamsipur, M. Hashemi, B. Hashemi, Liquid-phase microextraction of organophosphorus pesticides using supramolecular solvent as a carrier for ferrofluid, Talanta 160 (2016) 340–346.

DOI: 10.1016/j.talanta.2016.07.036

[9] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L.B. Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide, ACS Nano, 4 (2010) 4806–4814.

DOI: 10.1021/nn1006368

[10] T. Gadly, P.K. Mohapatra, D.K. Patre, R.B. Gujar, A. Gupta, A. Ballal, S.K. Ghosh, Superparamagnetic graphene oxide – magnetite nanoparticle composites for uptake of actinide ions from mildly acidic feeds, J. Chromatogr. A 1513 (2017) 18–26.

DOI: 10.1016/j.chroma.2017.07.008

[11] M. Niakan, M. Masteri-Farahani, H. Shekaari, S. Karimi, Pd supported on clicked cellulose-modified magnetite-graphene oxide nanocomposite for C-C coupling reactions in deep eutectic solvent, Carbohydr. Polym. 251 (2021).

DOI: 10.1016/j.carbpol.2020.117109

[12] S.M. Majidi, M.R. Hadjmohammadi, Alcohol-based deep eutectic solvent as a carrier of SiO2@Fe3O4 for the development of magnetic dispersive micro-solid-phase extraction method: Application for the preconcentration and determination of morin in apple and grape juices, diluted and acidic extract of dried onion and green tea infusion samples, J. Sep. Sci. 42 (2019) 2842–2850.

DOI: 10.1002/jssc.201900234

[13] N. Lamei, M. Ezoddin, M.S. Ardestani, K. Abdi, 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. 409 (2017) 6113–6121.

DOI: 10.1007/s00216-017-0547-8

[14] N. Mehrabi, U.F.A. Haq, M.T. Reza, N. Aich, Application of deep eutectic solvent for conjugation of magnetic nanoparticles onto graphene oxide for lead(II) and methylene blue removal, J. Environ. Chem. Eng. 8 (2020) 104222.

DOI: 10.1016/j.jece.2020.104222

[15] J. Zhao, G. Liang, X. Zhang, X. Cai, R. Li, X. Xie, Z. Wang, Coating magnetic biochar with humic acid for high efficient removal of fluoroquinolone antibiotics in water, Sci. Total Environ. 688 (2019) 1205–1215.

DOI: 10.1016/j.scitotenv.2019.06.287

[16] A.R. Zarei, M. Nedaei, S.A. Ghorbanian, Ferrofluid of magnetic clay and menthol based deep eutectic solvent: Application in directly suspended droplet microextraction for enrichment of some emerging contaminant explosives in water and soil samples, J. Chromatogr. A 1553 (2018) 32–42.

DOI: 10.1016/j.chroma.2018.04.023

[17] X. Song, R. Zhang, T. Xie, S. Wang, J. Cao, Deep eutectic solvent micro-functionalized graphene assisted dispersive micro solid-phase extraction of pyrethroid insecticides in natural products, Front. Chem. 7 (2019) 594.

DOI: 10.3389/fchem.2019.00594

[18] A. Ghasemi, M.R. Jamali, Z. Es'haghi, Ultrasound-assisted ferrofluid dispersive liquid-phase microextraction coupled with flame atomic absorption spectroscopy for the determination of cobalt in environmental samples, Anal. Lett. 54 (2021) 378–393.

DOI: 10.1080/00032719.2020.1765790

[19] N. Jamil, S.M. Khan, N. Ahsan, J. Anwar, A. Qadir, M. Zameer, U. Shafique, Removal of direct red 16 (textile dye) from industrial effluent by using feldspar, J. Chem. Soc. Pak. 36 (2014) 191–197.