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Bar adsorptive microextraction technique - application for the determination of pharmaceuticals in real matrices

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Abstract

In the present work, bar adsorptive microextraction using miniaturized devices (7.5 × 3.0 mm) coated with suitable sorbent phases, combined with microliquid desorption (100 μL) followed by high-performance liquid chromatography with diode array detection (BAμE-μLD/HPLC-DAD), is proposed for the determination of trace level of six pharmaceuticals (furosemide, mebeverine, ketoprofen, naproxen, diclofenac and mefenamic acid) in environmental water and urine matrices. By comparing ten distinct sorbent materials (five polymeric and five activated carbons), the polymer P5 proved to be the most suitable to achieve the best selectivity and efficiency. The solvent volume minimization in the liquid desorption stage demonstrated remarkable effectiveness, being more environmentally friendly, and simultaneously increased the microextraction enrichment factor two-fold. Assays performed through BAμE(P5, 0.9 mg)-μLD(100 μL)/HPLC-DAD on 25 mL of ultrapure water samples spiked at the 4.0 μg/L level yielded average recoveries ranging from 91.4% (furosemide) to 101.0% (ketoprofen) with good precision (RSD < 10.6%), under optimized experimental conditions. The analytical performance showed convenient detection limits (25.0 – 120.0 ng/L), good linear dynamic ranges (0.1 to 24.0 μg/L), appropriate determination coefficients (r 2 > 0.9983), and excellent repeatability through intraday (RSD < 10.4%)) and interday (RSD < 10.0%) assays. By using the standard addition methodology, the application of the present analytical approach on environmental waters and urine samples revealed the occurrence of trace levels of some pharmaceuticals. The solvent minimization during the back-extraction step associated with the miniaturization of BAμE devices proved to be a very promising analytical technology for static microextraction analysis.

BAμE operating under the floating sampling technology for the determination of pharmaceuticals in aqueous media.

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Acknowledgements

The authors wish to thank Fundação para a Ciência e a Tecnologia (Portugal) for funding (PEst-OE/QUI/UI0612/2013) and the PhD grants (SFRH/BD/69951/2010 and SFRH/BD/107892/2015).

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Authors and Affiliations

  1. Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, DQB/FCUL, Campo Grande Ed. C8, 1749-016, Lisboa, Portugal

    Carlos Almeida, Samir M. Ahmad & José Manuel F. Nogueira

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  1. Carlos Almeida
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  2. Samir M. Ahmad
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  3. José Manuel F. Nogueira
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Correspondence to José Manuel F. Nogueira.

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The study has been carried out in accordance with the ethical standards of the institutional research ethics committee.

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The authors declare that they have no conflict of interest.

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The human urine samples were collected from voluntary donors with their informed consent.

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Almeida, C., Ahmad, S.M. & Nogueira, J.M.F. Bar adsorptive microextraction technique - application for the determination of pharmaceuticals in real matrices. Anal Bioanal Chem 409, 2093–2106 (2017). https://doi.org/10.1007/s00216-016-0156-y

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  • DOI: https://doi.org/10.1007/s00216-016-0156-y

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