Abstract
Based on the synthesis of Fe3O4–MoS2 as magnetic solid-phase extraction adsorbent, a convenient, rapid, and effective method for extracting five fluoroquinolones (FQs) (lomefloxacin, ciprofloxacin, ofloxacin, sparfloxacin, and enrofloxacin) from eggs and detecting their contents by high-performance liquid chromatography using an ultraviolet-visible detector was established. The synthesized adsorbent was characterized by x-ray diffraction spectroscopy, scanning electron microscopy, and vibrating sample magnetometry. This study optimized the parameters (adsorbent, time of adsorption and desorption, eluent, sample solution, pH, and others) affecting the analytical performance of this method. Following optimization, the method provided good linearity from 2.5 to 300 μg L−1, correlation coefficients of determination from 0.9990 to 0.9997, limits of detection from 0.2 to 5.0 μg L−1, and limits of quantification from 0.7 to 17 μg L−1. The intra- and interday RSDs were less than 5%. The range of the spiked recoveries of FQs in eggs was 88.6 to 96.6%, and the RSDs were less than 5%.
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References
Aghagoli MJ, Beyki MH, Shemirani F (2017) Facile synthesis of Fe3O4/MoS2 nanohybrid for solid phase extraction of Ag (I) and Pb (II): kinetic, isotherm and thermodynamic studies. Int J Environ Anal Chem 97:1328–1351. https://doi.org/10.1080/03067319.2017.1414204
Ai K, Ruan C, Shen M, Lu L (2016) MoS2 nanosheets with widened interlayer spacing for high-efficiency removal of mercury in aquatic systems. Adv Funct Mater 26:5542–5549. https://doi.org/10.1002/adfm.201601338
Andreu V, Blasco C, Picó Y (2007) Analytical strategies to determine quinolone residues in food and the environment. Trac-Trend Anal Chem 26:534–556. https://doi.org/10.1016/j.trac.2007.01.010
Baghban N, Yilmaz E, Soylak M (2017) A magnetic MoS2-Fe3O4 nanocomposite as an effective adsorbent for dispersive solid-phase microextraction of lead (ii) and copper (ii) prior to their determination by faas. Microchim Acta 84:3969–3976
Cai L, He JF, Liu QH, Yao T, Chen L, Yan WS, Hu F, Jiang Y, Zhao Y, Hu T, Sun Z, Wei S (2015) Vacancy-induced ferromagnetism of MoS2 nanosheets. J Am Chem Soc 137:2622–2627
Carlucci G (1998) Analysis of fluoroquinolones in biological fluids by high-performance liquid chromatography. J Chromatogr A 812:343–367. https://doi.org/10.1016/S0021-9673(98)00274-X
Christodoulou EA, Samanidou VF, Papadoyannis IN (2007) Validation of an HPLC-UV method according to the European Union decision 2002/657/EC for the simultaneous determination of 10 quinolones in chicken muscle and egg yolk. J Chromatogr B Analyt Technol Biomed Life Sci 859:246–255. https://doi.org/10.1016/j.jchromb.2007.10.009
Chu P-S, Wang R-C, Chu HV (2002) Liquid chromatographic determination of fluoroquinolones in egg albumen and egg yolk of laying hens using fluorometric detection. J Agric Food Chem 50:4452–4455
Cui XQ, Zhang PJ, Yang XL, Yang MY, Zhou WF, Zhang SB, Gao H, Lu R (2015) β-CD/ATP composite materials for use in dispersive solid-phase extraction to measure (fluoro)quinolone antibiotics in honey samples. Anal Chim Acta 878:131–139. https://doi.org/10.1016/j.aca.2015.03.056
Dolan SP, Capar SG (2002) Multi-element analysis of food by microwave digestion and inductively coupled plasma-atomic emission spectrometry. J Food Compos Anal 15:593–615. https://doi.org/10.1006/jfca.2002.1064
Dong H, Xiao K (2017) Modified QuEChERS combined with ultra high performance liquid chromatography tandem mass spectrometry to determine seven biogenic amines in Chinese traditional condiment soy sauce. Food Chem 229:502–508. https://doi.org/10.1016/j.foodchem.2017.02.120
Dong H, Xiao KJ, Xian YP, Wu YL, Zhu L (2019) A novel approach for simultaneous analysis of perchlorate (ClO4 −) and bromate (BrO3 −) in fruits and vegetables using modified QuEChERS combined with ultrahigh performance liquid chromatography-tandem mass spectrometry. Food Chem 270:196–203. https://doi.org/10.1016/j.foodchem.2018.07.091
European Commission (2010) Commission regulation (EU) no 37/2010 of 22 December 2009 on pharmacologically active substances and their classification regarding maximum residue limits in foodstuffs of animal origin. Off J Eur Union 15:1–72
Gao Q, Zheng HB, Luo D, Ding J, Feng YQ (2012) Facile synthesis of magnetic one-dimensional polyaniline and its application in magnetic solid phase extraction for fluoroquinolones in honey samples. Anal Chim Acta 720:57–62. https://doi.org/10.1016/j.aca.2011.12.067
Gao XJ, Wang XF, Ouyang XP, Wen C (2016) Flexible superhydrophobic and superoleophilic MoS2 sponge for highly efficient oil-water separation. Sci Rep 6:27207
Geng XM, Zhang YL, Han Y, Li JX, Yang L, Benamara M, Chen L, Zhu H (2017) Two-dimensional water-coupled metallic MoS2 with nanochannels for ultrafast supercapacitors. Nano Lett 17:1825–1832
Han CL, Huang GR, Zhu DJ, Hu KH (2017) Facile synthesis of MoS2/Fe3O4 nanocomposite with excellent photo-Fenton-like catalytic performance. Mater Chem Phys 200:16–22. https://doi.org/10.1016/j.matchemphys.2017.07.065
Hassouan MK, Ballesteros O, Zafra A, Vilchez JL, Navalon A (2007) Multiresidue method for simultaneous determination of quinolone antibacterials in pig kidney samples by liquid chromatography with fluorescence detection. J Chromatogr B Analyt Technol Biomed Life Sci 859:282–288. https://doi.org/10.1016/j.jchromb.2007.10.002
He X, Wang GN, Yang K, Liu HZ, Wu XJ, Wang JP (2016) Magnetic graphene dispersive solid phase extraction combining high performance liquid chromatography for determination of fluoroquinolones in foods. Food Chem 221:1226–1231. https://doi.org/10.1016/j.foodchem.2016.11.035
Hernández-Arteseros JA, Barbosa J, Compañó R, Prat MD (2002) Analysis of quinolone residues in edible animal products. J Chromatogr A 945:1–24. https://doi.org/10.1016/S0021-9673(01)01505-9
Jimenez V, Companyo R, Guiteras J (2011) Validation of a method for the analysis of nine quinolones in eggs by pressurized liquid extraction and liquid chromatography with fluorescence detection. Talanta 85:596–606. https://doi.org/10.1016/j.talanta.2011.04.021
Krishna Kumar AS, Jiang SJ, Warchoł JK (2017) Synthesis and characterization of two-dimensional transition metal dichalcogenide magnetic MoS2@Fe3O4 nanoparticles for adsorption of Cr (VI)/Cr (III). ACS Omega 2:6187–6200
Kummerer K (2009) The presence of pharmaceuticals in the environment due to human use—present knowledge and future challenges. J Environ Manag 90:2354–2366. https://doi.org/10.1016/j.jenvman.2009.01.023
Lin T, Wang J, Guo LQ, Fu FF (2015) Fe3O4@MoS2 core–shell composites: preparation, characterization, and catalytic application. J Phys Chem C 119:13658–13664
Liu L, Zhou W (2017) MoS2 hollow microspheres used as a green lubricating additive for liquid paraffin. Tribol Int 114:315–321. https://doi.org/10.1016/j.triboint.2017.04.043
Liu ZG, Wang Y, Deng R, Yang LY, Yu SH, Xu SP, Xu W (2016) Fe3O4@graphene oxide@Ag particles for surface magnet solid-phase extraction surface-enhanced raman scattering (SMSPE-SERS): from sample pretreatment to detection all-in-one. ACS Appl Mater Interfaces 8:14160–14168
Lolo M, Pedreira S, Fente C, Vázquez BI, Franco CM, Cepeda A (2005) Study of enrofloxacin depletion in the eggs of laying hens using diphasic dialysis extraction/purification and determinative HPLC-MS analysis. J Agric Food Chem 53:2849–2852
Lombardo-Agüí M, García-Campaña AM, Cruces-Blanco C, Gámiz-Gracia L (2015) Determination of quinolones in fish by ultra-high performance liquid chromatography with fluorescence detection using QuEChERS as sample treatment. Food Control 50:864–868. https://doi.org/10.1016/j.foodcont.2014.10.027
Oliphant CM, Green GM (2002) Quinolones: a comprehensive review. Am Fam Physician 65:455–464
Ribeiro CC, Orlando RM, Rohwedder JJ, Reyes FG, Rath S (2016) Electric field-assisted solid phase extraction and cleanup of ionic compounds in complex food matrices: fluoroquinolones in eggs. Talanta 152:498–503. https://doi.org/10.1016/j.talanta.2016.02.047
Shi YT, Wu H, Wang CQ, Guo XZ, Du JL, Du LM (2016) Determination of polycyclic aromatic hydrocarbons in coffee and tea samples by magnetic solid-phase extraction coupled with HPLC-FLD. Food Chem 199:75–80. https://doi.org/10.1016/j.foodchem.2015.11.137
Shim JH, Lee MH, Kim MR, Lee CJ, Kim IS (2014) Simultaneous measurement of fluoroquinolones in eggs by a combination of supercritical fluid extraction and high pressure liquid chromatography. Biosci Biotechnol Biochem 67(6):1342–1348. https://doi.org/10.1271/bbb.67.1342
Song HJ, You SS, Jia XH, Yang J (2015) MoS2 nanosheets decorated with magnetic Fe3O4 nanoparticles and their ultrafast adsorption for wastewater treatment. Ceram Int 41:13896–13902. https://doi.org/10.1016/j.ceramint.2015.08.023
Spratt TE, Schultz SS, Levy DE, Chen D, Schlüter G, Williams GM (1999) Different mechanisms for the photoinduced production of oxidative DNA damage by fluoroquinolones differing in photostability. Chem Res Toxicol 12:809–815
Turel I (2002) The interactions of metal ions with quinolone antibacterial agents. Coord Chem Rev 232:27–47. https://doi.org/10.1016/S0010-8545(02)00027-9
Wang ZY, Mi BX (2017) Environmental applications of 2D molybdenum disulfide (MoS2) nanosheets. Environ Sci Technol 51:8229–8244
Wang KP, Wang J, Fan JT, Lotya M, O’Neill A, Fox D, Feng Y, Zhang X, Jiang B, Zhao Q, Zhang H, Coleman JN, Zhang L, Blau WJ (2013) Ultrafast saturable absorption of two-dimensional MoS2 nanosheets. ACS Nano 7:9260–9267
Wang K, Lin K, Huang X, Chen M (2017) A simple and fast extraction method for the determination of multiclass antibiotics in eggs using LC-MS/MS. J Agric Food Chem 65:5064–5073
Wu H, Gao NN, Zhang LZ, Li YR, Shi YT, Du LM (2015) Automated magnetic solid-phase extraction for synthetic food colorant determination. Food Anal Method 9:614–623
Wu H, Shi Y, Guo X, Zhao S, Du J, Jia H, Du L (2016) Determination and removal of sulfonamides and quinolones from environmental water samples using magnetic adsorbents. J Sep Sci 39:4398–4407. https://doi.org/10.1002/jssc.201600631
Wu Q, Li MN, Huang Z, Shao YM, Bai L, Zhou L (2017) Well-defined nanostructured core-shell magnetic surface imprinted polymers (Fe3O4@SiO2@MIPs) for effective extraction of trace tetrabromobisphenol A from water. J Ind Eng Chem 60:268–278. https://doi.org/10.1016/j.jiec.2017.11.013
Yan FW, Yang GW, Xiao KO, Li YY (2017) Surface-imprinted magnetic carboxylated cellulose nanocrystals for the highly selective extraction of six fluoroquinolones from egg samples. ACS Appl Mater Interfaces 9:1759–1769
Zhang Y, Chen P, Wen FF, Yuan B, Wang HG (2016a) Fe3O4 nanospheres on MoS2 nanoflake: electrocatalysis and detection of Cr(VI) and nitrite. J Electroanal Chem 761:14–20. https://doi.org/10.1016/j.jelechem.2015.12.004
Zhang YL, Yin ZF, Dai CM, Zhou XF, Chen W (2016b) Interfacial thermodynamics and kinetics of sorption of diclofenac on prepared high performance flower-like MoS2. J Colloid Interface Sci 481:210–219. https://doi.org/10.1016/j.jcis.2016.07.046
Zhang XD, Wang CC, Yang LY, Zhang W, Lin J, Li C (2017) Determination of eight quinolones in milk using immunoaffinity microextraction in a packed syringe and liquid chromatography with fluorescence detection. J Chromatogr B Analyt Technol Biomed Life Sci 1064:68–74. https://doi.org/10.1016/j.jchromb.2017.09.004
Zheng HB, Mo JZ, Zhang Y, Gao Q, Ding J, Yu QW, Feng YQ (2014) Facile synthesis of magnetic molecularly imprinted polymers and its application in magnetic solid phase extraction for fluoroquinolones in milk samples. J Chromatogr A 1329:17–23. https://doi.org/10.1016/j.chroma.2013.12.083
Zhou P, Huang LS, Zhou J, Jiang B, Zhao YM, Deng XH, Zhao Q, Li F (2017) Discovery of novel 4(1H)-quinolone derivatives as potential antiproliferative and apoptosis inducing agents. Bioorg Med Chem Lett 27:4185–4189. https://doi.org/10.1016/j.bmcl.2017.07.005
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Hao Wu declares that he has no conflict of interest. Yanli Liu declares that she has no conflict of interest. Jianzhong Chang declares that he has no conflict of interest. Bingxin Zhao declares that she has no conflict of interest. Yaoxing Huo declares that he has no conflict of interest. Zhuliang Wang declares that he has no conflict of interest. Yating Shi declares that she has no conflict of interest.
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Wu, H., Liu, Y., Chang, J. et al. Extraction of Five Fluoroquinolones in Eggs by Magnetic Solid-Phase Extraction with Fe3O4–MoS2 and Determination by HPLC-UV. Food Anal. Methods 12, 712–721 (2019). https://doi.org/10.1007/s12161-018-1404-x
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DOI: https://doi.org/10.1007/s12161-018-1404-x