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Water-compatible molecularly imprinted polymer for the selective recognition of fluoroquinolone antibiotics in biological samples

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Abstract

A novel water-compatible molecularly imprinted polymer (MIP), prepared with enrofloxacin (ENR) as the template, has been optimised for the selective extraction of fluoroquinolone antibiotics in aqueous media. The results of a morphological characterisation and selectivity tests of the polymer material for ENR and related derivatives are reported. High affinity for the piperazine-based fluoroquinolones marbofloxacin, ciprofloxacin, norfloxacin and ofloxacin was observed, whereas no retention was found for nonrelated antibiotics. Various parameters affecting the extraction efficiency of the polymer have been optimised to achieve selective extraction of the antibiotics from real samples and to reduce nonspecific interactions. These findings resulted in a MISPE/HPLC-FLD method allowing direct extraction of the analytes from aqueous samples with a selective wash using just 50% (v/v) organic solvent. The method showed excellent recoveries and precision when buffered urine samples fortified at five concentration levels (25–250 ng mL−1 each) of marbofloxacin, ciprofloxacin, norfloxacin, enrofloxacin and sarafloxacin were tested (53–88%, RSD 1–10%, n = 3). Moreover, the biological matrix of the aqueous samples did not influence the preconcentration efficiency of the fluoroquinolones on the MIP cartridges; no significant differences were observed between the recovery rates of the antibiotics in buffer and urine samples. The detection limits of the whole process range between 1.9 and 34 ng mL–1 when 5-mL urine samples are processed. The developed method has been successfully applied to preconcentration of norfloxacin in urine samples of a medicated patient, demonstrating the ability of the novel MIP for selective extraction of fluoroquinolones in urine samples.

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Abbreviations

MIP:

molecularly imprinted polymer

NIP:

nonimprinted polymer

MAA:

methacrylic acid

HEMA:

2-hydroxyethyl methacrylate

EDMA:

ethylene glycol dimethacrylate

ABDV:

2,2′-azobis(2,4-dimethylvaleronitrile)

FQs:

fluoroquinolones

ENR:

enrofloxacin

MAR:

marbofloxacin

SAR:

sarafloxacin

CIP:

ciprofloxacin

NOR:

norfloxacin

OFL:

ofloxacin

AMX:

amoxicillin

PEG:

penicillin G

CLX:

cloxacillin

CEP:

cephapirin

DAP:

dapsone

BZ:

benzoic acid

HPLC:

high-performance liquid chromatography

FLD:

fluorescence detector

DAD:

diode array detector

LLE:

liquid–liquid extraction

SFE:

supercritical fluid extraction

PLE:

pressurised liquid extraction

SPE:

solid-phase extraction

MISPE:

molecularly imprinted solid-phase extraction

MI-MSPD:

molecularly imprinted matrix solid-phase dispersion

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Acknowledgements

This work has been funded by the European Marie Curie Programme (MRTN-CT-2006–033873), the Spanish MEC (grant CTQ2006–15610-C02), the Madrid Regional Government (ref. S-0505/AMB/0374), the ESF, the ERDF and UCM (CCG07-UCM/AMB-2932). The authors thank Prof. M.J. Torralvo for the N2 adsorption studies.

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Authors and Affiliations

  1. Department of Analytical Chemistry, Faculty of Chemistry, Universidad Complutense de Madrid, 28040, Madrid, Spain

    Elena Benito-Peña, Sofia Martins & María Cruz Moreno-Bondi

  2. Department of Organic Chemistry, Faculty of Chemistry, Universidad Complutense de Madrid, 28040, Madrid, Spain

    Guillermo Orellana

Authors
  1. Elena Benito-Peña
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  2. Sofia Martins
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  3. Guillermo Orellana
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  4. María Cruz Moreno-Bondi
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Correspondence to María Cruz Moreno-Bondi.

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Benito-Peña, E., Martins, S., Orellana, G. et al. Water-compatible molecularly imprinted polymer for the selective recognition of fluoroquinolone antibiotics in biological samples. Anal Bioanal Chem 393, 235–245 (2009). https://doi.org/10.1007/s00216-008-2405-1

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  • DOI: https://doi.org/10.1007/s00216-008-2405-1

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