Abstract
A sensitive and selective method for separating fluoroquinolones (FQs) from bovine milk samples was successfully developed using montmorillonite magnetic molecularly imprinted polymers (MMMIPs) as adsorbents. MMMIPs were prepared using montmorillonite as carrier, fleroxacin (FLE) as template molecule, and Fe3O4 magnetite as magnetic component. MMMIPs possessed high adsorption capacity of 46.3 mg g−1 for FLE. A rapid and convenient magnetic solid-phase extraction procedure coupled with capillary electrophoresis was established with MMMIPs as adsorbents for simultaneous and selective extraction of four FQs in bovine milk samples. Limits of detection ranged between 12.9 and 18.8 μg L−1, and the RSDs were between 1.8 % and 8.6 %. The proposed method was successfully applied to spike bovine milk samples with recoveries of 92.7 %–108.6 %.
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References
Andreu V, Blasco C, Picó Y (2007) Analytical strategies to determine quinolone residues in food and the environment. Trends Anal Chem 26:534–556
Brown SA (1996) Fluoroquinolones in animal health. J Vet Pharmacol Ther 19:1–14
Commission of the European Communities (2010) Off J Eur Commun L15:1–72
US Food and Drug Administration (FDA) (2006) Code of Federal regulation. Food and Drugs 6, Part 556
Pulgarín JAM, Molina AA, Muñoz SR (2011) Rapid chemiluminescent determination of enrofloxacin in eggs and veterinary drugs. Anal Lett 44:2194–2208
Chen B, Wang W, Huang Y (2012) Cigarette filters as adsorbents of solid-phase extraction for determination of fluoroquinolone antibiotics in environmental water samples coupled with high-performance liquid chromatography. Talanta 88:237–243
Sun X, Wang J, Li Y, Yang J, Jin J, Shah SM, Chen J (2014) Novel dummy molecularly imprinted polymers for matrix solid-phase dispersion extraction of eight fluoroquinolones from fish samples. J Chromatogr A 1359:1–7
Parrilla Vázquez MM, Parrilla Vázquez P, Martínez Galera M, Gil García MD (2012) Determination of eight fluoroquinolones in groundwater samples with ultrasound- assisted ionic liquid dispersive liquid–liquid microextraction prior to high-performance liquid chromatography and fluorescence detection. Anal Chim Acta 748:20–27
Rodríguez E, Navarro-Villoslada F, Benito-Peña E, Marazuela MD, Moreno-Bondi MC (2011) Multiresidue determination of ultratrace levels of fluoroquinolone antimicrobials in drinking and aquaculture water samples by automated online molecularly imprinted solid phase extraction and liquid chromatography. Anal Chem 83:2046–2055
Huang X, Wang Y, Liu Y, Yuan D (2013) Preparation of magnetic poly(vinylimidazole-co-divinylbenzene) nanoparticles and their application in the trace analysis of fluoroquinolones in environmental water samples. J Sep Sci 36:3210–3219
Aguilera-Luiz M, Vidal JLM, Romero-González R, Frenich AG (2008) Multi-residue determination of veterinary drugs in milk by ultra-high-pressure liquid chromatography-tandem mass spectrometry. J Chromatogr A 1205:10–16
Blasco C, Picó Y (2012) Development of an improved method for trace analysis of quinolones in eggs of laying hens and wildlife species using molecularly imprinted polymers. J Agr Food Chem 60:11005–11014
Bourdat-Deschamps M, Leang S, Bernet N, Daudin JJ, Nelieu S (2014) Multiresidue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: Optimization and matrix effects reduction by quick, easy, cheap, effective, rugged, and safe extraction. J Chromatogr A 1349:11–23
Alothman ZA, Dawod M, Kim J, Chung DS (2012) Single-drop microextraction as a powerful pretreatment tool for capillary electrophoresis: a review. Anal Chim Acta 739:14–24
Lara FJ, Garcia-Campana AM, Ales-Barrero F, Bosque-Sendra JM, Garcia-Ayuso LE (2006) Multiresidue method for the determination of quinolone antibiotics in bovine raw milk by capillary electrophoresis-tandem mass spectrometry. Anal Chem 78:7665–7673
Piñero MY, Garrido-Delgado R, Bauza R, Arce L, Valcarcel M (2012) Easy sample treatment for the determination of enrofloxacin and ciprofloxacin residues in raw bovine milk by capillary electrophoresis. Electrophoresis 33:2978–2986
Morales-Cid G, Cárdenas S, Simonet BM, Valcárcel M (2009) Fully automatic sample treatment by integration of microextraction by packed sorbents into commercial capillary electrophoresis-mass spectrometry equipment: application to the determination of fluoroquinolones in urine. Anal Chem 81:3188–3193
Tang C, Tan J, Wang C, Peng X (2014) Determination of perfluoro-octanoic acid and perfluoro-octane sulfonate in cooking oil and pig adipose tissue using reversed-phase liquid–liquid extraction followed by high performance liquid chromatography tandem mass spectrometry. J Chromatogr A 1341:50–56
Wägli P, Chang YC, Homsy A, Hvozdara L, Herzig HP, de Rooij NF (2013) Microfluidic droplet-based liquid–liquid extraction and on-chip IR spectroscopy detection of cocaine in human saliva. Anal Chem 85:7558–7565
Yan H, Qiao J, Wang H, Yang G, Row KH (2011) Molecularly imprinted solid-phase extraction combined with ultrasound-assisted dispersive liquid–liquid microextraction for the determination of four Sudan dyes in sausage samples. Analyst 136:2629–2634
Wierucka M, Biziuk M (2014) Application of magnetic nanoparticles for magnetic solid-phase extraction in preparing biological, environmental and food samples. Trends Anal Chem 59:50–58
González-Mariño I, Quintana JB, Rodríguez I, Gonzalez-Diez M, Cela R (2012) Screening and selective quantification of illicit drugs in wastewater by mixed-mode solid-phase extraction and quadrupole-time-of-flight liquid chromatography-mass spectrometry. Anal Chem 84:1708–1717
Mirnaghi F, Pawliszyn J (2012) Reusable solid-phase microextraction coating for direct immersion whole-blood analysis and extracted blood spot sampling coupled with liquid chromatography-tandem mass spectrometry and direct analysis in real time–tandem mass spectrometry. Anal Chem 84:8301–8309
Xu S, Zhang X, Sun Y, Yu D (2013) Microwave-assisted preparation of monolithic molecularly imprinted polymeric fibers for solid phase microextraction. Analyst 138:2982–2987
Cui X, Bao L, Gan J (2013) Solid-phase microextraction (SPME) with stable isotope calibration for measuring bioavailability of hydrophobic organic contaminants. Environ Sci Technol 47:9833–9840
Wang L, Duan C, Wu D, Guan Y (2014) Quantification of endogenous brass inosteroids in sub-gram plant tissues by in-line matrix solid-phase dispersion-tandem solid phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1359:44–51
Vela-Soria F, Ballesteros O, Camino-Sánchez FJ, Zafra-Gómez A, Ballesteros L, Navalón A (2015) Matrix solid phase dispersion for the extraction of selected endocrine disrupting chemicals from human placental tissue prior to UHPLC-MS/MS analysis. Microchem J 118:32–39
Lan H, Gan N, Pan D, Hu F, Li T, Long N, Shen H, Feng Y (2014) Development of a novel magnetic molecularly imprinted polymer coating using porous zeolite imidazolate framework-8 coated magnetic iron oxide as carrier for automated solid phase microextraction of estrogens in fish and pork samples. J Chromatogr A 1365:35–44
Zheng H, Mo J, Zhang Y, Gao Q, Ding J, Yu Q, Feng Y (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
Yao G, Liang R, Huang C, Wang Y, Qiu J (2013) Surface plasmon resonance sensor based on magnetic molecularly imprinted polymers amplification for pesticide recognition. Anal Chem 85:11944–11951
Griffete N, Li H, Lamouri A, Redeuilh C, Chen K, Dong C, Nowak S, Ammar S, Mangeney C (2012) Magnetic nanocrystals coated by molecularly imprinted polymers for the recognition of bisphenol A. J Mater Chem 22:1807–1811
Zhang Z, Tan W, Hu Y, Li G, Zan S (2012) Microwave synthesis of gibberellin acid 3 magnetic molecularly imprinted polymer beads for the trace analysis of gibberellin acids in plant samples by liquid chromatography-mass spectrometry detection. Analyst 137:968–977
Kan X, Zhao Q, Shao D, Geng Z, Wang Z, Zhu J (2010) Preparation and recognition properties of bovine hemoglobin magnetic molecularly imprinted polymers. J Phys Chem B 114:3999–4004
Parisi OI, Morelli C, Puoci F, Saturnino C, Caruso A, Sisci D, Trombino GE, Picci N, Sinicropi MS (2014) Magnetic molecularly imprinted polymers (MMIPs) for carbazole derivative release in targeted cancer therapy. J Mater Chem B 2:6619–6625
Zhao M, Zhang C, Zhang Y, Guo X, Yan H, Zhang H (2014) Efficient synthesis of narrowly dispersed hydrophilic and magnetic molecularly imprinted polymer microspheres with excellent molecular recognition ability in a real biological sample. Chem Commun 50:2208–2210
Gao R, Kong X, Wang X, He X, Chen L, Zhang Y (2011) Preparation and characterization of uniformly sized molecularly imprinted polymers functionalized with core–shell magnetic nanoparticles for the recognition and enrichment of protein. J Mater Chem 21:17863–17871
Serrate D, De Teresa JM, Marquina C, Marzo J, Saurel D, Cardoso FA, Cardoso S, Freitas PP, Ibarra MR (2012) Quantitative biomolecular sensing station based on magnetoresistive patterned arrays. Biosens Bioelectron 35:206–212
Bhattacharyya KG, Gupta SS (2008) Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review. Adv Colloid Interf 140:114–131
Abolghasemi MM, Parastari S, Yousefi V (2015) Microextraction of phenolic compounds using a fiber coated with a polyaniline-montmorillonite nanocomposite. Microchim Acta 182:273–280
Abolghasemi MM, Parastari S, Yousefi V (2014) Polypyrrole-montmorillonite nanocomposite as sorbent for solid-phase microextraction of phenolic compounds in water. J Sep Sci 37:3526–3532
Zarpon L, Abate G, dos Santos LBO, Masini JC (2006) Montmorillonite as an adsorbent for extraction and concentration of atrazine, propazine, deethylatrazine, deisopropylatrazine, and hydroxyatrazine. Anal Chim Acta 579:81–87
Wu PX, Dai YP, Long H, Zhu NW, Jai P, Wu JH, Dang Z (2012) Characterization of organo-montmorillonites and comparison for Sr (II) removal: equilibrium and kinetic studies. Chem Eng J 191:288–296
Jafari MT, Saraji M, Sherafatm H (2014) Polypyrrole/montmorillonite nanocomposite as a new solid phase microextraction fiber combined with gas chromatography-corona discharge ion mobility spectrometry for the simultaneous determination of diazinon and fenthion organophosphorus pesticides. Anal Chim Acta 814:69–78
Liu X, Yin J, Zhu L, Zhao G, Zhang H (2011) Evaluation of a magnetic polysulfone microcapsule containing organic modified montmorillonite as a novel solid-phase extraction sorbent with chlorophenols as model compounds. Talanta 85:2451–2457
Larraza I, López-Gónzalez M, Corrales T, Marcelo G (2012) Hybrid materials: magnetite–polyethylenimine–montmorillonite, as magnetic adsorbents for Cr (VI) water treatment. J Colloid Interface Sci 385:24–33
Chen D, Li W, Wu Y, Zhu Q, Lu Z, Du G (2013) Preparation and characterization of chitosan/montmorillonite magnetic microspheres and its application for the removal of Cr (VI). Chem Eng J 221:8–15
Ho C, Sin DWM, Tang HPO, Chung PK, Siu SMP (2004) Determination and on-line clean-up of (fluoro)quinolones in bovine milk using column-switching liquid chromatography fluorescence detection. J Chromatogr A 1061:123–131
He H, Dong C, Li B, Dong J, Bo T, Wang T, Yu Q, Feng Y (2014) Fabrication of enrofloxacin imprinted organic–inorganic hybrid mesoporous sorbent from nanomagnetic polyhedral oligomeric silsesquioxanes for the selective extraction of fluoroquinolones in milk samples. J Chromatogr A 1361:23–33
Ibarra IS, Rodríguez JA, Páez-Hernández ME, Santos EM, Miranda JM (2012) Determination of quinolones in milk samples using a combination of magnetic solid-phase extraction and capillary electrophoresis. Electrophoresis 33:2041–2048
Springer V, Jacksén J, Ek P, Lista AG, Emmer Å (2014) Determination of fluoroquinolones in bovine milk samples using a pipette-tip SPE step based on multiwalled carbon nanotubes prior to CE separation. J Sep Sci 37:158–164
Xiao J, Chen Y, Xu J (2014) Plasma grafting montmorillonite/iron oxide composite with b-cyclodextrin and its application for high-efficient decontamination of U(VI). J Ind Eng Chem 20:2830–2839
Sun Y, Wang Q, Chen C, Tan X, Wang X (2012) Interaction between Eu(III) and graphene oxide nanosheets investigated by batch and extended X-ray absorption fine structure spectroscopy and by modeling techniques. Environ Sci Technol 46:6020–6027
Hsieh S, Huang BY, Hsieh SL, Wu CC, Wu CH, Lin PY, Huang YS, Chang CW (2010) Green fabrication of agar-conjugated Fe3O4 magnetic nanoparticles. Nanotechnology 21:445601
Hao Y, Gao R, Shi L, Liu D, Tang Y, Guo Z (2015) Water-compatible magnetic imprinted nanoparticles served as solid-phase extraction sorbents for selective determination of trace 17 beta-estradiol in environmental water samples by liquid chromatography. J Chromatogr A 1396:7–16
Xie X, Pan X, Han S, Wang S (2015) Development and characterization of magnetic molecularly imprinted polymers for the selective enrichment of endocrine disrupting chemicals in water and milk samples. Anal Bioanal Chem 407:1735–1744
Anirudhan TS, Divya PL, Nima J (2013) Silylated montmorillonite based molecularly imprinted polymer for the selective binding and controlled release of thiamine hydrochloride. React Funct Polym 73:1144–1155
Giakisikli G, Anthemidis AN (2013) Magnetic materials as sorbents for metal/ metalloid preconcentration and/or separation: a review. Anal Chim Acta 789:1–16
Wagenlehner FME, Weidner W, Sörgel F, Naber KG (2005) The role of antibiotics in chronic bacterial prostatitis. Int J Antimicrob Agents 26:1–7
Gao W, Chen G, Chen Y, Zhang X, Yin Y, Hu Z (2011) Application of single drop liquid–liquid–liquid microextraction for the determination of fluoroquinolones in human urine by capillary electrophoresis. J Chromatogr B 879:291–295
Acknowledgments
This study was supported by the National Natural Science Foundation of China (21464006), the Major Projects of Department of Education of Guangdong Province (2014KZDXM074), the Project of Department of Education of Guangdong Province (2013KJCX0191 and 2014KTSCX193), the Project of Science and Technology Innovation Project of Zhaoqing City (2013 F013), the Special Projects of University Talent Introduction of Guangdong Province(2013197), the Science and Technology Planning Project of Zhaoqing High-Technology Zone (2012B01003002), and the Natural Science Foundation of Zhaoqing University (201318).
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Wang, H., Liu, Y., Wei, S. et al. Selective extraction and determination of fluoroquinolones in bovine milk samples with montmorillonite magnetic molecularly imprinted polymers and capillary electrophoresis. Anal Bioanal Chem 408, 589–598 (2016). https://doi.org/10.1007/s00216-015-9140-1
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DOI: https://doi.org/10.1007/s00216-015-9140-1