Kill two birds with one stone: Selective and fast removal and sensitive determination of oxytetracycline using surface molecularly imprinted polymer based on ionic liquid and ATRP polymerization

Abstract

Oxytetracycline (OTC) residue in food and environment has potential threats to ecosystem and human health, thus its sensitive monitoring and effective elimination are very important. In this work, a new molecularly imprinted polymer (MIP) composite was prepared through atom transfer radical polymerization by using OTC as template, gold nanoparticles modified carbon nanospheres (Au-CNS) as supporter, ionic liquids (IL) as functional monomer and cross-linking agent. The obtained MIP-IL@Au-CNS composite was characterized by Fourier transform infrared absorption spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. It displayed high imprinting factor (5.50) and adsorption capacity (56.7 mg g−1), and could achieved the adsorption equilibrium in short time (about 15 min). Results also illustrated that the adsorption process basically conformed to the quasi-second-order kinetic model and Freundlich model, and MIP-IL@Au-CNS could be recycled at least 5 times. Furthermore, a sensitive OTC electrochemical sensor was developed by combining MIP-IL@Au-CNS with IL-modified carbon nanocomposites (IL@N-rGO-MWCNT). The resulting sensor demonstrated a linear response to OTC in the wide range of 0.02–20 μM, and the detection limit was down to 5 nM. It also had the advantages of high selectivity, fast elution/regeneration and simple construction procedure. The sensor had been applied to the detection of real samples, and acceptable recovery (96.4%−106%) and RSD (3.2%−6.2%) were obtained. This work expands the application of IL-based MIP in pollutant monitoring and enriching.