A hollow porous molecularly imprinted polymer as a sorbent for the extraction of 7 macrolide antibiotics prior to their determination by HPLC-MS/MS

Abstract

A hollow porous molecularly imprinted polymer (HPMIP) is described for use in dispersive solid phase extraction of macrolide antibiotics (MACs). The HPMIP was prepared by using spiramycin as the template, methacrylic acid as the functional monomer, and mesoporous MCM-41 (Mobile Composition of Matter No. 41; with a size of about 100 nm) as a sacrificial support. The sorbent was characterized by Fourier transform infrared spectrometry, transmission electron microscopy, nitrogen adsorption and thermo-gravimetric analysis. Several parameters affecting the extraction efficiency were optimized. The material has a large surface area (359 m·g), and most recognition sites are located on the surface of the HPMIPs. This results in high binding capacity (120 μmol·g) and fast binding (20 min) in comparison to either MCM-41-core surface MIPs or solid MIPs. The method was applied to the extraction of the MACs azithromycin, spiramycin, tilmicosin, tylosin, clarithromycin, roxithromycin and josamycin from spiked honey. The recoveries, determined by HPLC-MS/MS, ranged from 88.0% to 117% at the three spiking levels tested (1, 5 and 20 μg·kg). Intra-day and inter-day assay precision at three spiking levels are <10.7% (for n = 6) and 12.6% (n = 3), respectively. The limits of detection are between 3 and 17 ng·kg. This indicates the superiority of the method in selective extraction of macrolides even from complex matrices. Graphical abstract Hollow porous molecularly imprinted polymers using spiramycin as the template are shown to be viable dispersive solid phase extraction adsorbents for selective enrichment of macrolide antibiotics in honey products prior to their quantitation by HPLC-MS/MS.

Preparation and Application of Molecularly Imprinted Monolithic Extraction Column for the Selective Microextraction of Multiple Macrolide Antibiotics from Animal Muscles

“…As a hydrogen bond donator, the carboxyl group of MAA was more likely to participate in the formation of hydrogen bonds with abundant hydroxyl groups of the template. As previous studies discovered [25,26,27], with the 4:1 ratio of MAA to template, the polymers gained high adsorption capacity and specificity to MALs. Based on this ratio, other polymerization parameters were investigated while using single factor analysis.…”

“…When compared with novel extraction strategies using MIP technology, the method had lower LODs than the HPLC methods based on multi-walled carbon nanotubes MISPE (MWNTs-MIPSE) [28] and magnetic MISPE (MMISPE) [27]. Two papers described the determination of multiple macrolides in animal foodstuffs by LC-MS/MS based on MISPE [29] and hollow porous MIP-DSPE (HPMIP-DSPE) [26]. Although the LODs of the method that was developed were slightly higher than those of the MISPE method, the recoveries of this method were much better than the latter.…”

“…Current attempts for the synthesis of MALs-MIP include traditional approaches (bulk, precipitation, or suspension) [23,24,25] and some novel strategies that are based on hollow porous material [26], magnetic particles [27], and multi-walled carbon nanotubes [28]. These MIPs were applied to the selective extraction of MALs in animal tissues [27,29] and honey samples [26] based on molecularly imprinted solid-phase extraction (MISPE), magnetic solid-phase extraction (MSPE), and dispersive solid-phase extraction (DSPE). However, traditional MIPs need to be ground, sieved, and sometimes stabilizer is necessary in polymerization, which is time-consuming.…”

Strategies of molecular imprinting-based solid-phase extraction prior to chromatographic analysis

“…Ji et al used mesoporous MCM-41 as hard sacrificial support for fabrication of HMIPs for the simultaneous extraction of seven macrolide antibiotics [144]. The MCM-41 possessed superb surface areas, adjustable pore sizes, large pore volumes, and most importantly, can easily be dissolved in hydrogen fluoride solution.…”

Recent Advances in Molecular-Imprinting-Based Solid-Phase Extraction of Antibiotics Residues Coupled With Chromatographic Analysis

“…It can overcome the disadvantages of low binding capacity and difficulty in elution of traditional MIPs. Core-shell structured MIPs are the major type of surface imprinting MIPs, owing to the increased surface area and larger binding capacity, and thus, they are widely used for detecting antibiotic residues (Ji et al, 2018;Liu et al, 2018;Negarian et al, 2019;Qin et al, 2019;Zhu et al, 2019a).…”