Molecularly imprinted polymer-hollow fiber microextraction of hydrophilic fluoroquinolone antibiotics in environmental waters and urine samples

Abstract

In the present work, the preparation of a new selective molecularly imprinted polymer (MIP) for the family of fluoroquinolones (FQs) in the pores of polypropylene hollow fibers (HFs) is proposed. The resulting MIP-HFs, which combine solid-phase microextraction (SPME) and molecular imprinting technologies, were used to develop a selective microextraction methodology (MIP-HFM) to determine selected FQs danofloxacin, norfloxacin, enrofloxacin and ciprofloxacin in real samples of environmental and biological interest.Measurements during the optimization of the MIP-HFM and its application to the analyses of real samples were performed by HPLC-UV and HPLC-MS/MS. In order to establish optimum rebinding conditions, the effect of key experimental parameters such as loading media, extraction time and stirring-rate were studied. The developed MIP composites exhibited recognition properties towards the selected hydrophilic antibiotics in non-polar media (toluene) and in polar protic systems such as methanol and methanol/water solutions, up to 20% water content.Recoveries by the developed method for all FQs tested in surface water, groundwater and urine spiked with the analytes of interest at two different concentration levels were within 9.4–24.5 %, with a relative standard deviation, generally <20% (n = 3). The detection limits were within 0.1–10 μg L−1, depending upon the antibiotic and the type of sample.