Adsorption-controlled preparation of molecularly imprinted hybrid composites for selective extraction of tetracycline residues from honey and milk

Molecularly imprinted organic–inorganic hybrid composite materials (MIP-HCMs) with controlled swelling and adsorption properties were prepared through copolymerization and the sol–gel process by using doxycycline (DC) as the template molecule, methacrylic acid (MAA) as a functional monomer, methacryloxypropyltrimethoxysilane (KH-570) as a coupling agent and TEOS as an inorganic precursor. By means of changing polymerization conditions as well as the copolymerization ratio of the inorganic precursor and the organic functional monomer, the properties of sorbents can be adjusted for different needs. So the effect of preparation conditions on the structure of the material was studied. The polymer group, thermal stability, adsorption and selectivity characteristics, and the volume swelling degree of the MIP-HCMs were characterized by FTIR, TGA, and dynamic adsorption and swelling experiments, respectively. It was observed that the MIP-HCMs exhibited the highest selectivity (4.9), maximum adsorption capacity (58.2 mg g−1) and good thermal stability. The obtained MIP-HCM was used as an adsorbent for solid-phase extraction of tetracyclines from the milk and honey samples. The average recoveries of three tetracycline antibiotics (DC, tetracycline and chlortetracycline) were obtained in the range of 74.7–115.5% with the precision of 2.1–4.9%. The limits of detection and quantitation of the proposed method were in the range of 4.9–15.3 μg kg−1 and 16.6–51.0 μg kg−1 for the milk samples, and 8.3–15.1 μg kg−1 and 18.3–50.2 μg kg−1 for the honey samples, respectively.