Water-compatible molecularly imprinted polymer for the selective recognition of fluoroquinolone antibiotics in biological samples.
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.
Department of Analytical Chemistry, Faculty of Chemistry, Universidad Complutense de Madrid, 28040, Madrid, Spain.
Elena
E
Benito-Peña
Sofia
S
Martins
Guillermo
G
Orellana
María Cruz
MC
Moreno-Bondi
D000900:Anti-Bacterial Agents / Q000737:chemistry / Q000652:urine*; D002851:Chromatography, High Pressure Liquid; D000077422:Enrofloxacin; D005026:Ethylene Glycols / Q000138:chemical synthesis / Q000737:chemistry*; D024841:Fluoroquinolones / Q000737:chemistry; D006801:Humans; D006863:Hydrogen-Ion Concentration; D008689:Methacrylates / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D009643:Norfloxacin / Q000737:chemistry / Q000652:urine*; D013050:Spectrometry, Fluorescence; D013997:Time Factors; D014867:Water / Q000737:chemistry*
D000900:Anti-Bacterial Agents; D005026:Ethylene Glycols; D024841:Fluoroquinolones; D008689:Methacrylates; C502776:poly(methacrylic acid-ethylene glycol dimethacrylate); D014867:Water; D000077422:Enrofloxacin; D009643:Norfloxacin