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Analytical and Bioanalytical Chemistry

, Volume 393, Issue 1, pp 235–245 | Cite as

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

  • Elena Benito-Peña
  • Sofia Martins
  • Guillermo Orellana
  • María Cruz Moreno-BondiEmail author
Original Paper

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.

Keywords

Water-compatible molecularly imprinted polymers Fluoroquinolones Antibiotics Solid-phase extraction Urine samples 

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

Notes

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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Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  • Elena Benito-Peña
    • 1
  • Sofia Martins
    • 1
  • Guillermo Orellana
    • 2
  • María Cruz Moreno-Bondi
    • 1
    Email author
  1. 1.Department of Analytical Chemistry, Faculty of ChemistryUniversidad Complutense de MadridMadridSpain
  2. 2.Department of Organic Chemistry, Faculty of ChemistryUniversidad Complutense de MadridMadridSpain

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