“一锅法”制备氨基碳纳米管功能化磁性纳米粒子及其在谷物和蔬菜中苯氧羧酸类除草剂测定中的应用

Phenoxyacetic acid herbicides (PAs) are widely used to control the growth of broad-leaf weeds in corn, tobacco, etc. The presence of PAs in plants even at low concentrations (at the ng/L to μg/L scale) may induce severe effects and lead to human health risks. Hence, a sensitive and reliable method for the determination of PAs at trace levels in cereals and vegetables is highly desired. Magnetic solid-phase extraction (MSPE) has attracted considerable attention on account of its benefits such as ease of separation, less solvent consumption, and good service life. In this study, aminated carbon nanotube-modified magnetic nanoparticles (NH(2)-CNTs@M) were prepared by a convenient and simple “one-pot” strategy and employed as the adsorbent for the MSPE of PAs in crops. The fabrication procedure is very convenient. In detail, the aminated carbon nanotubes, Fe(Ⅱ), Fe(Ⅲ), and isopropanol were mixed in one pot with mechanical stirring and reacted for 2.0 h at 80 ℃. The spectroscopic properties, morphology, and magnetic properties of the synthetic adsorbent were characterized by Fourier Transform-infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results revealed that the size of Fe(3)O(4), diameter of NH(2)-CNTs, and the magnetic saturation values of NH(2)-CNTs@M were 30 nm, 40 nm, and 44.2 emu/g, respectively. Additionally, the results of FT-IR and TEM characterization confirmed the successful fabrication of NH(2)-CNTs@M by this “one-pot” hydrothermal approach. The NH(2)-CNTs@M displayed satisfactory capability to capture PAs through π-π, hydrophobic, and hydrogen-bonding interactions. To realize the best extraction performance, the key parameters, including the amount of adsorbent, formic acid concentration in the eluent, adsorption and desorption time, sample pH, and ionic strength in the sample matrices, were inspected and studied in detail. The optimal conditions were as follows: amount of NH(2)-CNTs@M, 30 mg; desorption solvent, 0.5 mL acetonitrile containing 2.0% (v/v) formic acid; adsorption and desorption times, 8.0 and 3.0 min, respectively; the sample pH was adjusted to 6.0, and no salt was added to the sample. Under the optimized extraction conditions, a sensitive, quick, and environmentally friendly method for the determination of the studied PAs in cereal and vegetable samples was established by the combination of NH(2)-CNTs@M/MSPE with high performance liquid chromatography-diode array detection (HPLC-DAD). The enrichment factors for the studied PAs varied from 73 to 90. The limits of detection (S/N=3) for the PAs in the cereal and vegetable matrixes were in the ranges of 0.32-1.6 μg/kg and 0.53-1.6 μg/kg, respectively; and the limits of quantification (S/N=10) for the PAs in the cereal and vegetable matrixes were 0.94-4.8 μg/kg and 1.6-4.8 μg/kg. The developed method also showed wide linear ranges and good precision. Finally, the established NH(2)-CNTs@M/MSPE-HPLC-DAD approach was applied to measure trace levels of PAs in cereals and vegetables, and good fortified recoveries (72.3% to 113%) and repeatability (RSDs below 10%) were obtained. The established approach has several advantages over the existing methods, such as high analytical speed, low LODs, and eco-friendliness.