Synthesis and application of molecularly imprinted poly(methacrylic acid)–silica hybrid composite material for selective solid-phase extraction and high-performance liquid chromatography determination of oxytetracycline residues in milk

A novel molecularly imprinted organic–inorganic hybrid composite material (MIP-HCM) was developed based on molecular imprinting technique in combination with hybrid composite synthesis and sol–gel technology for selective solid-phase extraction (SPE) of tetracyclines residues in milk. The MIP-HCM was prepared using oxytetracycline as the template, methacrylic acid as organic functional monomer, tetraethoxysilane as inorganic precursor and methacryloxypropyltrimethoxysilane as the coupling agent. Synthesis conditions are optimized by changing some factors to obtain sorbent with the controllable adsorption capacity, selectivity, hardness and toughness. Binding study demonstrated that the imprinted hybrid composites showed excellent affinity and high selectivity to oxytetracycline. An enrichment factor of 18.8 along with a good sample clean-up was obtained under the optimized SPE conditions. The average recoveries of three tetracyclines antibiotics spiked milk at 0.1, 0.2 and 0.5 mg kg−1 were in the range of 80.9–104.3% with the precision of 1.5–5.0%. The limits of detection and quantitation of the proposed method were in a range of 4.8–12.7 μg kg−1 and 16.0–42.3 μg kg−1, respectively.

► A molecularly imprinted hybrid composite material (MIP-HCM) was synthesized.
► Synthesis conditions are optimized by changing some factors, such as components.
► The structural characteristics and adsorption properties of the MIP-HCM were investigated.
► Three tetracycline antibiotics residues in milk were separated and detected by MISPE-HPLC with better clean up and enrichment.