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Rapid Determination of Trace Sulfonamides in Milk by Graphene Oxide-Based Magnetic Solid Phase Extraction Coupled with HPLC–MS/MS

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Abstract

A simple and rapid method based on magnetic solid-phase extraction (MSPE) combined with high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (HPLC–MS/MS) was used for the determination of 15 sulfonamides from milk samples. The extraction and cleanup used a graphene oxide-based magnetic nanocomposite (Fe3O4@GO) as an adsorbent. Various experimental parameters that could affect the extraction efficiencies, such as the amount of Fe3O4@GO, the extraction time, the ionic strength of sample solution, and the type of eluent, were investigated. Under optimized experimental conditions, good linearity was observed in the range of 2.0 to 100.0 μg L−1 for all of the analytes, with correlation coefficients (R2) ranging from 0.994 to 0.999. The limits of detection for the method ranged between 0.02 and 0.13 μg L−1. Mean values of the relative standard deviation of intraday and interday precision ranging from 1.0 to 7.3 % and from 1.7 to 8.1 % were obtained, respectively. The average recoveries were between 73.4 and 97.4 % at three different spiked levels. It was confirmed that the Fe3O4@GO nanocomposite was an effective MSPE material for use in sulfonamide analyses in milk samples.

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References

  • Arroyo-Manzanares N, Gámiz-Gracia L, García-Campaña AM (2014) Alternative sample treatments for the determination of sulfonamides in milk by HPLC with fluorescence detection. Food Chem 143:459–464

    Article  CAS  Google Scholar 

  • Chen L, Zhou T, Zhang Y, Lu Y (2013) Rapid determination of trace sulfonamides in fish by graphene-based SPE coupled with UPLC/MS/MS. Anal Methods 5:4363–4370

    Article  CAS  Google Scholar 

  • Chen H, Gao B, Li H (2015) Removal of sulfamethoxazole and ciprofloxacin from aqueous solutions by graphene oxide. J Hazard Mater 282:201–207

    Article  CAS  Google Scholar 

  • European Union (1999) Commission Regulation 281/96 of 14 February 1996 amending Annexes I and III to Council Regulation (EEC) No. 2377/90 laying down a Community procedure for establishment of maximum residue limits of veterinary medical products in foodstuff of animal origin. Off J L37:9

    Google Scholar 

  • Gao Q, Luo D, Ding J, Feng Y (2010) Rapid magnetic solid-phase extraction based on magnetite/silica/poly (methacrylic acid-co- ethylene glycol dimethacrylate) composite microspheres for the determination of sulfonamide in milk samples. J Chromatogr A 1217:5602–5609

    Article  CAS  Google Scholar 

  • Garrido Frenich A, Aguilera-Luiz Mdel M, Martínez Vidal JL, Romero-González R (2010) Comparison of several extraction techniques for multiclass analysis of veterinary drugs in eggs using ultra-high pressure liquid chromatography–tandem mass spectrometry. Anal Chim Acta 661:150–160

    Article  CAS  Google Scholar 

  • Han Q, Wang Z, Xia J, Chen S, Zhang X, Ding M (2012) Facile and tunable fabrication of Fe3O4/graphene oxide nanocomposites and their application in the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples. Talanta 101:388–395

    Article  CAS  Google Scholar 

  • Heller DN, Ngoh MA, Donoghue D, Podhorniak L, Righter H, Thomas MH (2002) Identification of incurred sulfonamide residues in eggs: methods for confirmation by liquid chromatography–tandem mass spectrometry and quantitation by liquid chromatography with ultraviolet detection. J Chromatogr B 774:39–52

    Article  CAS  Google Scholar 

  • Hu S, Cao W, Da J, Dai H, Cao J, Ye L, Li X, Chu C (2015) Dispersive micro solid-phase extraction with graphene oxide for the determination of phenolic compounds in dietary supplements by ultra high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry. Food Anal Methods 8:833–840

    Article  Google Scholar 

  • Huang D, Deng C, Zhang X (2014) Functionalized magnetic nanomaterials as solid-phase extraction adsorbents for organic pollutants in environmental analysis. Anal Methods 6:7130–7141

    Article  CAS  Google Scholar 

  • Hyun-Hee C, Jung-Bin L, Yun-Hee C, Kwang-Geun L (2009) Analysis of sulfonamide and quinolone antibiotic residues in Korean milk using microbial assays and high performance liquid chromatography. Food Chem 113:297–301

    Article  Google Scholar 

  • Ibarra IS, Miranda JM, Rodriguez JA, Nebot C, Cepeda A (2014) Magnetic solid phase extraction followed by high-performance liquid chromatography for the determination of sulphonamides in milk samples. Food Chem 157:511–517

    Article  CAS  Google Scholar 

  • Li H, Sun H, Zhang J, Pang K (2013) Highly sensitive and simultaneous determination of sixteen sulphonamide antibiotics, four acetyled metabolites and trimethoprim in meat by rapid resolution liquid chromatography-tandem mass spectrometry. Food Control 31:359–365

    Article  CAS  Google Scholar 

  • Luo Y, Shi Z, Gao Q, Feng Y (2011) Magnetic retrieval of graphene: extraction of sulfonamide antibiotics from environmental water samples. J Chromatogr B 1218:1353–1358

    Article  CAS  Google Scholar 

  • Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun ZZ, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814

    Article  CAS  Google Scholar 

  • Meng Z, Shi Z, Liang S, Dong X, Li H, Sun H (2015) Residues investigation of fluoroquinolones and sulphonamides and their metabolites in bovine milk by quantification and confirmation using ultra-performance liquid chromatography-tandem mass spectrometry. Food Chem 174:597–605

    Article  CAS  Google Scholar 

  • Pan S, Zhou L, Zhao Y, Chen X, Shen H, Cai M, Jin M (2014) Amine-functional magnetic polymer modified graphene oxide as magnetic solid-phase extraction materials combined with liquid chromatography-tandem mass spectrometry for chlorophenols analysis in environmental water. J Chromatogr A 1362:34–42

    Article  CAS  Google Scholar 

  • Pereira R, Eustáquia de Freitas E, Fabiano de Alkimim J, Azevedo E, Vasconcellos D, Augusti R (2012) Development and validation of a method for the determination of sulfonamides in animal feed by modified QuEChERS and LC-MS/MS analysis. Food Control 28:192–198

    Article  Google Scholar 

  • Reeves VB (1999) Confirmation of multiple sulfonamide residues in bovine milk by gas chromatography-positive chemical ionization mass spectrometry. J Chromatogr B 723:127–137

    Article  CAS  Google Scholar 

  • Roach JA, DiBussolo JM, Krynitsky A, Noonan GO (2011) Evaluation and single laboratory validation of an on-line turbulent flow extraction tandem mass spectrometry method for melamine in infant formula. J Chromatogr A 218:4284–4290

    Article  Google Scholar 

  • Sitko R, Zawisza B, Malicka E (2013) Graphene as a new sorbent in analytical chemistry. Trends Anal Chem 51:33–43

    Article  CAS  Google Scholar 

  • Soto-Chinchilla JJ, García-Campaña AM, Gámiz-Gracia L, Ruces-Blanco CC (2006) Application of capillary zone electrophoresis with large-volume sample stacking to the sensitive determination of sulfonamides in meat and ground water. Electrophoresis 27:4060–4068

    Article  CAS  Google Scholar 

  • Sun J, Liang Q, Han Q, Zhang X, Ding M (2015) One-step synthesis of magnetic graphene oxide nanocomposite and its application in magnetic solid phase extraction of heavy metal ions from biological samples. Talanta 132:557–563

    Article  CAS  Google Scholar 

  • Synaridou ME, Sakkas VA, Stalikas CD, Albanis TA (2014) Evaluation of magnetic nanoparticles to serve as solid-phase extraction sorbents for the determination of endocrine disruptors in milk samples by gas chromatography mass spectrometry. J Chromatogr A 1348:71–79

    Article  CAS  Google Scholar 

  • Tso J, Dutta S, Inamdar S, Aga DS (2011) Simultaneous analysis of free and conjugated estrogens, sulfonamides, and tetracyclines in runoff water and soils using solid-phase extraction and liquid chromatography-tandem mass spectrometry. J Agric Food Chem 59:2213–2222

    Article  CAS  Google Scholar 

  • Wang L, Wu J, Wang Q, He C, Zhou L, Wang J, Pu Q (2012) Rapid and sensitive determination of sulfonamide residues in milk and chicken muscle by microfluidic chip electrophoresis. J Agric Food Chem 60:1613–1618

    Article  CAS  Google Scholar 

  • Won SY, Lee CH, Chang HS, Kim SO, Lee SH, Kim DS (2011) Monitoring of 14 sulfonamide antibiotic residues in marine products using HPLC-PDA and LC-MS/MS. Food Control 22:1101–1107

    Article  CAS  Google Scholar 

  • Wu MC, Deokar AR, Liao JH, Shi PY, Ling YC (2013) Graphene-based photothermal agent for rapid and effctive killing of bacteria. ACS Nano 7:1281–1290

    Article  CAS  Google Scholar 

  • Zeng S, Gan N, Weideman-Mera R, Cao Y, Li T, Sang W (2013) Enrichment of polychlorinated biphenyl 28 from aqueous solutions using Fe3O4 grafted graphene oxide. Chem Eng J 218:108–115

    Article  CAS  Google Scholar 

  • Zhang H, Zhang Y, Wang S (2008) Development of flow-through and dip-stick immunoassays for screening of sulfonamide residues. J Immunol Methods 337:1–6

    Article  CAS  Google Scholar 

  • Zheng H, Mo J, Zhang Y, Gao Q, Ding J, Yu Q, Fen 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

    Article  CAS  Google Scholar 

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    Authors and Affiliations

    1. College of Food Science and Engineering, Northwest A&F University, Yangling, Shaanxi, 712100, People’s Republic of China

      Yutang Wang, Laping Liu, Chunxia Xiao, Lin Chen, Peng Yang, Qian Liu, Jianlong Wang & Xuebo Liu

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    1. Yutang Wang
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    2. Laping Liu
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    3. Chunxia Xiao
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    4. Lin Chen
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    5. Peng Yang
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    6. Qian Liu
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    7. Jianlong Wang
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    8. Xuebo Liu
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    Correspondence to Xuebo Liu.

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    Funding

    This study was funded by the Basic Science Research Foundation (grant number: 2452015203) of Northwest A&F University.

    Conflict of Interest

    Yutang Wang declares that he has no conflict of interest.

    Laping Liu declares that he has no conflict of interest.

    Chunxia Xiao declares that she has no conflict of interest.

    Lin Chen declares that she has no conflict of interest.

    Peng Yang declares that he has no conflict of interest.

    Qian Liu declares that she has no conflict of interest.

    Jianlong Wang declares that he has no conflict of interest.

    Xuebo Liu declares that he has no conflict of interest.

    Ethical Approval

    This article does not contain any studies with human participants or animals performed by any of the authors.

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    Informed consent was obtained from all individual participants included in the study.

    This article does not contain any studies with human participants or animals performed by any of the authors.

    Additional information

    Yutang Wang and Laping Liu contributed equally to this work.

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    Wang, Y., Liu, L., Xiao, C. et al. Rapid Determination of Trace Sulfonamides in Milk by Graphene Oxide-Based Magnetic Solid Phase Extraction Coupled with HPLC–MS/MS. Food Anal. Methods 9, 2521–2530 (2016). https://doi.org/10.1007/s12161-016-0433-6

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    • DOI: https://doi.org/10.1007/s12161-016-0433-6

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