Multiresidue analysis of fluoroquinolone antimicrobials in chicken meat by molecularly imprinted solid-phase extraction and high performance liquid chromatography

• Novel MIP beads selective to FQs were prepared using a combinatorial approach.
• MISPE–HPLC–FLD/MISPE–HPLC–MS/MS methods are proposed for determination of 6 FQs in chicken.
• LOQs are below maximum residue limits allowed by the EU in chicken muscle.
• Recoveries for the legislated FQs in chicken muscle samples ranged from 72 to 101% with RSDs <7% using MISPE–HPLC–FLD.

This paper describes the synthesis of novel molecularly imprinted polymer (MIP) micro-beads for the selective extraction (MISPE) of six fluoroquinolone (FQ) antibiotics (enrofloxacin, ciprofloxacin, lomefloxacin, danofloxacin, sarafloxacin and norfloxacin) from chicken muscle samples and further analysis by high-performance liquid chromatography (HPLC) with fluorescence (FLD) or mass spectrometry (MS) detection. A combinatorial screening approach has been applied to select the optimal functional monomer and cross-linker formulation for polymer synthesis. The MIP prepared using enoxacin (ENOX) as the template – a mixture of methacrylic acid (MAA) and trifluoromethacrylic acid (TFMAA) as functional monomers and ethylene glycol dimethacrylate (EDMA) as the cross-linker – showed superior FQ recognition properties than the rest of the materials generated. MIP spherical particles were prepared using silica beads as sacrificial scaffolds. The polymers were packed in solid phase extraction (SPE) cartridges. The optimized MISPE–HPLC method allows the extraction of the antimicrobials from aqueous samples followed by a selective washing with acetonitrile/water (0.005% TFA, pH = 3.0), 20:80 (v/v) and elution with 5% trifluoroacetic acid in methanol. Optimum MISPE conditions led to recoveries of the target FQs in chicken muscle samples ranging between 68 and 102% and precisions in the 3–4% range (RSD, n = 18). The method has been validated according to European Union Decision 2002/657/EC, in terms of linearity, accuracy, precision, selectivity, decision limit (CCα) and detection capability (CCβ) by HPLC–FLD and HPLC–MS/MS. The limits of detection were improved using HPLC–MS/MS analysis and ranged between 0.2 and 2.7 μg kg−1 (S/N = 3) for all the FQs tested.