Abstract

A new method for the isolation and enrichment of ofloxacin enantiomers from fish samples was developed using magnetic molecularly imprinted polymers (MMIPs). These polymers can be easily collected and rapidly separated using an external magnetic field, and also exhibit a high specific recognition for ofloxacin enantiomers. The preparation of amino-functionalized MMIPs was carried out via suspension polymerization and a ring-opening reaction using rac-ofloxacin as a template, ethylenediamine as an active group, glycidyl methacrylate and methyl methacrylate as functional monomers, divinylbenzene as a cross-linker, and Fe3O4 nanoparticles as magnetic cores. The characteristics of the MMIPs were assessed using transmission electron microscopy (TEM), X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) measurements. Furthermore, the adsorption properties were determined using Langmuir and Freundlich isotherm models. The conditions for use of these MMIPs as magnetic solid-phase extraction (MSPE) sorbents, including pH, adsorption time, desorption time, and eluent, were investigated in detail. An extraction method using MMIPs coupled with high performance liquid chromatography (HPLC) was developed for the determination of ofloxacin enantiomers in fish samples. The limits of quantitation (LOQ) for the developed method were 0.059 and 0.067 μg∙mL−1 for levofloxacin and dextrofloxacin, respectively. The recovery of ofloxacin enantiomers ranged from 79.2% ± 5.6% to 84.4% ± 4.6% and ofloxacin enantiomers had good linear relationships within the concentration range of 0.25–5.0 μg∙mL−1 (R2 > 0.999). The obtained results demonstrate that MSPE-HPLC is a promising approach for preconcentration, purification, and simultaneous separation of ofloxacin enantiomers in biomatrix samples.

Highlights

  • In recent years, the differences in the pharmacology and pharmokinetics of enantiomers of chiral drugs have received increasing attention [1,2]

  • molecularly imprinted polymers (MMIPs) were synthesized by suspension polymerization

  • The MMIPs were synthesized by suspension polymerization according to the literature procedure [32,33,34,35] with a minor modification

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Summary

Introduction

The differences in the pharmacology and pharmokinetics of enantiomers of chiral drugs have received increasing attention [1,2]. Efficient, and fast pretreatment strategies using molecular imprinting techniques [15,16] or magnetic solid-phase extraction (MSPE) [17,18,19,20] have received more attention. New amino-functionalized MMIPs as MSPE sorbents were prepared for the extraction of OFL enantiomers in fish samples. A method based on MSPE coupled with chiral-HPLC analysis was successfully optimized for the separation and determination of OFL enantiomers in fish samples. This proposed technique was shown to be a reliable and effective analytical method for determination of trace amounts of chiral drugs in biomatrix samples. Enantiopure templates can be used for the preparation of imprinted polymers with enantiodiscriminative features that could be successfully applied for enantioseparation and drug delivery in the future [26,27]

Synthesis and Characterization of MMIPs
Magnetic
Effect of pH Value
Optimisation adsorption onto onto MMIPs
Adsorption Time
Kinetic equations and of rate constants theeffect adsorption of OFL onto
Desorption Conditions
Reusability of MMIPs
Imprinting Effects of MMIPs and MNIPs on OFL Adsorption
Application
Application of MMIPsoftothe
Materials
Chromatographic Conditions
Preparation of Rac-Ofloxacin MMIPs
Characterization
Adsorption Studies
Separation Enrichment and Determination of OFL Enantiomers in Fish Samples
Conclusions

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