Food Analytical Methods

, Volume 12, Issue 1, pp 271–281 | Cite as

Rapid Determination of Sulfonamides in Chicken Muscle and Milk Using Efficient Graphene Oxide-Based Monolith On-Line Solid-Phase Extraction Coupled with Liquid Chromatography–Tandem Mass Spectrometry

  • Xue-Lei Chen
  • Lian-Feng Ai
  • Ya-Qing Cao
  • Qi-Xun Nian
  • Ye-Qing Jia
  • Yu-Lan Hao
  • Man-Man WangEmail author
  • Xue-Sheng Wang


A graphene oxide-incorporated monolithic column was fabricated and developed as an on-line solid-phase extraction sorbent coupled with LC-MS/MS for the automatic and fast determination of 16 sulfonamides in chicken muscle and milk samples. The proposed hybrid sorbent was easily produced from graphene oxide and a single crosslinker of ethylene glycol dimethacrylate. It gave favorable properties including uniformer structure, larger specific surface area, and enhanced column efficiency compared to the neat polymer monolith. Loading and eluting solutions affecting the on-line SPE were studied in detail. Under the optimized conditions, the on-line solid phase extraction coupled with LC-MS/MS method was achieved in 23 min. The developed method exhibited good linearity in the range of 1–100 μg/kg for sulfonamides in milk samples, and 2–200 μg/kg in chicken muscle samples, with r ranging from 0.993 to 0.999. The detection limits (S/N = 3) were 0.3 μg/kg in milk and 0.6 μg/kg in chicken muscle. The spiked recoveries were in the range of 70.3–98.5% and 79.0–108.0%, with a precision of 5.19–9.37% and 4.04–8.57%, respectively. Furthermore, the graphene oxide-incorporated monolithic sorbent allowed more than 450 extraction cycles without any loss in the extraction efficiency. The developed method was successfully applied for the determination of 16 sulfonamides in milk and chicken muscle samples.


Graphene oxide On-line solid-phase extraction Sulfonamides Milk Chicken muscle 



This work was supported by the National Natural Science Foundation of China (no. 21305028), the Natural Science Foundation of Hebei Province, China (no. H2017209232 and no. H2016209018), the Research Foundation of the Education Bureau of Hebei Province, China (no. ZD2018014), and the Training Foundation of the North China University of Science and Technology (no. JQ201717).

Compliance with Ethical Standards

Conflict of Interest

Xue-Lei Chen declares no competing financial interest.

Lian-Feng Ai declares no competing financial interest.

Ya-Qing Cao declares no competing financial interest.

Qi-Xun Nian declares no competing financial interest.

Ye-Qing Jia declares no competing financial interest.

Yu-Lan Hao declares no competing financial interest.

Man-Man Wang declares no competing financial interest.

Xue-Sheng Wang declares no competing financial interest.

Ethical Approval

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

Informed Consent

Not applicable.

Supplementary material

12161_2018_1358_MOESM1_ESM.doc (64 kb)
ESM 1 (DOC 63 kb)
12161_2018_1358_Fig5_ESM.png (349 kb)

(PNG 349 kb)

12161_2018_1358_MOESM2_ESM.tif (933 kb)
High resolution image (TIF 933 kb)


  1. Austrian Agency for Health and Food Safety (2016) Annual veterinary report. https://wwwagesat/service/service-tiergesundheit/jahresberichte-berichte folder/veterinaerjahresbericht-2016/ Accessed 26 June 2018
  2. Baran W, Adamek E, Ziemiańska J, Sobczak A (2011) Effects of the presence of sulfonamides in the environment and their influence on human health. J Hazard Mater 196:1–15CrossRefGoogle Scholar
  3. Chen L, Zhang X, Sun L, Xu Y, Zeng Q, Wang H, Xu H, Yu A, Zhang H, Ding L (2009) Fast and selective extraction of sulfonamides from honey based on magnetic molecularly imprinted polymer. J Agric Food Chem 57:10073–10080CrossRefGoogle Scholar
  4. Chen X, Hai X, Wang J (2016) Graphene/graphene oxide and their derivatives in the separation/isolation and preconcentration of protein species: a review. Anal Chim Acta 922:1–10CrossRefGoogle Scholar
  5. Cheong CK, Hajeb P, Jinap S, Ismail-Fitry MR (2010) Sulfonamides determination in chicken meat products from Malaysia. Food Res Int 17:885–892Google Scholar
  6. Codex Alimentarius Commission (2017) CAC/MRL 2. Maximum residue limits (MRLs) and risk management recommendations (RMRs) for residues of veterinary drugs in foods http://wwwfaoorg/fao-who-codexalimentarius/codex-texts/dbs/vetdrugs/veterinary-drugs/zh/ Accessed 26 June 2018
  7. Cui B, Guo B, Wang H, Zhang D, Liu H, Bai L, Yan H, Han D (2018) Graphene oxide-based composite monolith as new sorbent for the on-line solid phase extraction and high performance liquid chromatography determination of β-sitosterol in food samples. Talanta 186:200–205CrossRefGoogle Scholar
  8. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2009) The chemistry of graphene oxide. Chem Soc Rev 39:228–240CrossRefGoogle Scholar
  9. Dreyer DR, Ruoff RS, Bielawski CW (2010) From conception to realization: an historical account of graphene and some perspectives for its future. Angew Chem Int Ed 49:9336–9344CrossRefGoogle Scholar
  10. European Community (2014) Council regulation no. 2377/90 of EEC establishment of maximum residue limits of veterinary medicinal products in foodstuffs of animal origin. Accessed 26 June 2018
  11. Franco MS, Padovan RN, Fumes BH, Lanças FM (2016) An overview of multidimensional liquid phase separations in food analysis. Electrophoresis 37:1768–1783CrossRefGoogle Scholar
  12. Fumes BH, Silva MR, Andrade FN, Nazario CED, Lanças FM (2015) Recent advances and future trends in new materials for sample preparation. TrAC Trends Anal Chem 7:9–25CrossRefGoogle Scholar
  13. Geim AK (2009) Graphene: status and prospects. Science 324:1530–1534CrossRefGoogle Scholar
  14. Hu S, Zhao M, Xi Y, Mao Q, Zhou X, Chen D, Yan P (2017) Nontargeted screening and determination of sulfonamides: a dispersive micro solid-phase extraction approach to the analysis of milk and honey samples using liquid chromatography–high-resolution mass spectrometry. J Agric Food Chem 65:1984–1991CrossRefGoogle Scholar
  15. Kechagia M, Samanidou V, Kabir A, Furton KG (2018) One-pot synthesis of a multi-template molecularly imprinted polymer for the extraction of six sulfonamide residues from milk before high-performance liquid chromatography with diode array detection. J Sep Sci 41:723–731CrossRefGoogle Scholar
  16. Li Y, Tolley HD, Lee ML (2010) Monoliths from poly(ethylene glycol) diacrylate and dimethacrylate for capillary hydrophobic interaction chromatography of proteins. J Chromatogr A 1217:4934–4945CrossRefGoogle Scholar
  17. Liu Q, Shi J, Zeng L, Wang T, Cai Y, Jiang G (2011) Evaluation of graphene as an advantageous adsorbent for solid-phase extraction with chlorophenols as model analytes. J Chromatogr A 1218:197–204CrossRefGoogle Scholar
  18. Lu J, Wang M, Li Y, Deng C (2012) Facile synthesis of TiO2/graphene composites for selective enrichment of phosphopeptides. Nanoscale 4:1577–1580CrossRefGoogle Scholar
  19. Lu Y, Cheng Z, Liu C, Cao X (2016) Determination of sulfonamides in fish using a modified quechers extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry. Food Anal Methods 9:1857–1866CrossRefGoogle Scholar
  20. Masini JC, Svec F (2017) Porous monoliths for on-line sample preparation: a review. Anal Chim Acta 964:24–44CrossRefGoogle Scholar
  21. Matuszewski BK, And MLC, Chavezeng CM (2003) Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS. Anal Chem 75:3019–3030CrossRefGoogle Scholar
  22. Neu HC (1992) The crisis in antibiotic resistance. Science 257:1064–1073CrossRefGoogle Scholar
  23. Nischang I, Causon TJ (2016) Porous polymer monoliths: from their fundamental structure to analytical engineering applications. TrAC Trends Anal Chem 75:108–117CrossRefGoogle Scholar
  24. Pan J, Zhang C, Zhang Z, Li G (2014) Review of online coupling of sample preparation techniques with liquid chromatography. Anal Chim Acta 815:1–15CrossRefGoogle Scholar
  25. Rogeberg M, Malerod H, Roberg-Larsen H, Aass C, Wilson SR (2014) On-line solid phase extraction-liquid chromatography, with emphasis on modern bioanalysis and miniaturized systems. J Pharm Biomed Anal 87:120–129CrossRefGoogle Scholar
  26. Russo M, Dugo P, Fanali C, Dugo L, Zoccali M, Mondello L, Gara LD (2018) Use of an online extraction technique coupled to liquid chromatography for determination of caffeine in coffee, tea, and cocoa. Food Anal Methods 11:2637–2644. CrossRefGoogle Scholar
  27. Schwaiger B, König J, Lesueur C (2018) Development and validation of a multi-class UHPLC-MS/MS method for determination of antibiotic residues in dairy products. Food Anal Methods 11:1417–1434CrossRefGoogle Scholar
  28. Sereshti H, Khosraviani M, Samadi S, Aminifazl MS (2014) Simultaneous determination of theophylline, theobromine and caffeine in different tea beverages by graphene-oxide based ultrasonic assisted dispersive micro solid-phase extraction combined with HPLC-UV. RSC Adv 4:47114–47120CrossRefGoogle Scholar
  29. Sitko R, Zawisza B, Malicka E (2013) Graphene as a new sorbent in analytical chemistry. TrAC Trends Anal Chem 51:33–43CrossRefGoogle Scholar
  30. Tong S, Liu Q, Li Y, Zhou W, Jia Q, Duan T (2012) Preparation of porous polymer monolithic column incorporated with graphene nanosheets for solid phase microextraction and enrichment of glucocorticoids. J Chromatogr A 1253:22–31CrossRefGoogle Scholar
  31. U.S. Department of Health and Human Services (2014) Antibiotic resistance threats in the United States. Accessed 26 June 2018
  32. Wang MM, Yan XP (2012) Fabrication of graphene oxide nanosheets incorporated monolithic column via one-step room temperature polymerization for capillary electrochromatography. Anal Chem 84:39–44CrossRefGoogle Scholar
  33. World Health Organization (2015) Tackling antibiotic resistance from a food safety perspective in Europe. Accessed 26 June 2018
  34. Xia L, Liu L, Lv X, Qu F, Li G, You J (2017) Towards the determination of sulfonamides in meat samples: a magnetic and mesoporous metal-organic framework as an efficient sorbent for magnetic solid phase extraction combined with high-performance liquid chromatography. J Chromatogr A 1500:24–31CrossRefGoogle Scholar
  35. Yoshikawa S, Nagano C, Kanda M, Hayashi H, Matsushima Y, Nakajima T, Tsuruoka Y, Nagata M, Koike H, Sekimura K, Hashimoto T, Takano I, Shindo T (2017) Simultaneous determination of multi-class veterinary drugs in chicken processed foods and muscle using solid-supported liquid extraction clean-up. J Chromatogr B 1057:15–23CrossRefGoogle Scholar
  36. Yuan Y, Sun N, Yan H, Han D, Row KH (2016) Determination of indometacin and acemetacin in human urine via reduced graphene oxide-based pipette tip solid-phase extraction coupled to HPLC. Microchim Acta 183:799–804CrossRefGoogle Scholar
  37. Yusuf M, Elfghi FM, Zaidi SA, Abdullah EC, Khan MA (2015) ChemInform abstract: applications of graphene and its derivatives as an adsorbent for heavy metal and dye removal: a systematic and comprehensive overview. RSC Adv 46:50392–50420CrossRefGoogle Scholar
  38. Zhang BT, Zheng X, Li HF, Lin JM (2013) Application of carbon-based nanomaterials in sample preparation: a review. Anal Chim Acta 784:1–17CrossRefGoogle Scholar
  39. Zhou C, Chen X, Du Z, Li G, Xiao X, Cai Z (2017) A hybrid monolithic column based on boronate-functionalized graphene oxide nanosheets for online specific enrichment of glycoproteins. J Chromatogr A 1498:90–98CrossRefGoogle Scholar
  40. Zhou J, Xu JJ, Cong JM, Cai ZX, Zhang JS, Wang JL, Ren YP (2018) Optimization for quick, easy, cheap, effective, rugged and safe extraction of mycotoxins and veterinary drugs by response surface methodology for application to egg and milk. J Chromatogr A 1532:20–29. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Public HealthNorth China University of Science and TechnologyTangshanChina
  2. 2.Hebei Entry–Exit Inspection and Quarantine BureauShijiazhuangChina

Personalised recommendations