Multi-residue analysis of sulfonamide antibiotics in honey samples by on-line solid phase extraction using molecularly imprinted polymers coupled to liquid chromatography-tandem mass spectrometry

Abstract

This work reports the development of a sensitive and automated online solid phase extraction method using molecularly imprinted polymers (MISPE) coupled to high performance liquid chromatography–tandem mass spectrometry (LC–MS/MS) (HPLC), for the identification and quantification of six sulfonamide antibiotics, namely sulfapiridyne, sulfadoxine, sulfaquinoxaline, sulfacetamide, sulfachloropyridazine and sulfamonomethoxine in honey samples from the Cuban market. The samples were hydrolyzed in acidic media to release the sugar-bound sulfonamides before injection into the preconcentration system. Polymer composition was selected using a combinatorial approach. Several parameters affecting the performance of the MISPE method were optimized to reduce nonspecific binding with the non-imprinted polymer and achieve a selective rebinding of the target antimicrobials. Method validation was performed according to Commission Decision 2002/657/EC in terms of linearity, recoveries, precision, specificity, decision limit (CC_α) and detection capability (CC_β). Intraday recoveries at three concentration levels (1, 10 and 20 μg Kg-1) were between 84.3 and 104.7% (RSD < 11.6%) while interday average recoveries were in the ranges 65.5–119.3% (RSDs < 10.4%). The values of CC_α and CC_β values were in the ranges 0.1–4.2 and 0.2–4.4 μg kg⁻¹, respectively. The limits of detection and quantitation for the investigated sulfonamides ranged from 0.004–1.050 µg kg⁻¹ and 0.014–3.499 µg kg⁻¹, respectively. The method described has been applied to the analysis of honey samples from Cuban producers.

GRAPHICAL ABSTRACT

Keywords:

• Antibiotics
• decision 2002/657/EC
• honey
• HPLC-MS/MS
• sulfonamides

Acknowledgments

Authors like to thank to Beekeeping Research Center (Ministry of Agriculture, Cuba) for allowing the use of their own research laboratories and instruments; to the University of Havana for the support and use of its instrumental facilities located at University Laboratory of Composition and Characterization of Substances. Finally, we acknowledge the NMR Research Support Centre and the National Center for Electron Microscopy at Complutese University of Madrid for instrumental support. Authors also like to thank Prof. María Cruz Moreno-Bondi and Prof Guillermo Orellana from University Complutense of Madrid for the English revision of the manuscript and comments about ¹H-NMR results respectively.

Additional information

Funding

Authors like to thank to Beekeeping Research Center (Ministry of Agriculture, Cuba) for providing the funds for this project.