Superparamagnetic Fe3 O4 @SiO2 core-shell composite nanoparticles for the mixed hemimicelle solid-phase extraction of benzodiazepines from hair and wastewater samples before high-performance liquid chromatography analysis.

Magnetic Fe3 O4 /SiO2 composite core-shell nanoparticles were synthesized, characterized, and applied for the surfactant-assisted solid-phase extraction of five benzodiazepines diazepam, oxazepam, clonazepam, alprazolam, and midazolam, from human hair and wastewater samples before high-performance liquid chromatography with diode array detection. The nanocomposite was synthesized in two steps. First, Fe3 O4 nanoparticles were prepared by the chemical co-precipitation method of Fe(III) and Fe(II) as reaction substrates and NH3 /H2 O as precipitant. Second, the surface of Fe3 O4 nanoparticles was modified with shell silica by Stober method using tetraethylorthosilicate. The Fe3 O4 /SiO2 composite were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. To enhance their adsorptive tendency toward benzodiazepines, cetyltrimethylammonium bromide was added, which was adsorbed on the surface of the Fe3 O4 /SiO2 nanoparticles and formed mixed hemimicelles. The main parameters affecting the efficiency of the method were thoroughly investigated. Under optimum conditions, the calibration curves were linear in the range of 0.10-15 μgmL(-1) . The relative standard deviations ranged from 2.73 to 7.07%. The correlation coefficients varied from 0.9930 to 0.9996.