A core-shell amino-functionalized glycidyl methacrylate magnetic molecularly imprinted polymer (MIP) was synthesized by the suspension polymerization/surface imprinting method and characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), mercury porosimetry, nitrogen gas adsorption–desorption, and elemental analysis. This MIP was used as the sorbent in dispersive solid-phase microextraction (DSPME) of aniline from textile wastewater prior to high-performance liquid chromatography-mass spectrometry (HPLC-MS) measurements. Since aniline is toxic and a probable human carcinogen, its determination in water is of great significance. This is a challenging task because aniline is usually present at trace levels. The effects of different DSPME variables on the preconcentration efficiency have been studied by using the Plackett–Burman screening design of experiments (DoE) followed by response surface methodology optimization using the Box-Behnken design. Thus, DoE enabled the investigation of several variables simultaneously. Under optimized conditions, aniline was effectively and selectively separated by a small amount of the DSPME sorbent and detected in real textile wastewater samples. The method detection limit of 1 ng mL−1 was attained, with good method linearity and acceptable recovery and precision. The results showed that the studied MIP could be a reliable DSPME sorbent for efficiently analyzing trace aniline in real wastewater samples.
An amino-functionalized magnetic macroporous copolymer of glycidyl methacrylate (GM) and ethylene glycol (E) dimethacrylate (m-poly(GME)-deta) was synthesized, fully characterized, and used to investigate the adsorption of vanadium (V) oxyanions from aqueous solutions (Ci = 0.5 mM) in a batch system at room temperature (298 K). Pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich, and intra-particle diffusion (IPD) models were used to analyze the kinetic data. The study showed that sorption is rapid, i.e., the sorption half-time is approximately one minute. Initially, the sorption process primarily involved surface sorbent particles, and it was best described by the PSO model. However, after saturation of the surface active sites is attained, the sorption rate decreases significantly because of limitations of the diffusion rate, which is then primarily controlled by the IPD process. The sorption process is favorable in the pH range of 3–6 due to the strong electrostatic interactions between the absorption centers of copolymer and vanadium (V) oxyanions. In the stated pH range, deta absorption centers with two and three protonated N atoms are in equilibrium as studied by quantum chemical modeling. Among V(V) species present in diluted aqueous media, the adsorption of H2VO4− ions dominates.
A new magnetic amino-functionalized polymeric sorbent based on glycidyl methacrylate was synthesized and used in the separation of chromium Cr(VI) oxyanions sorption from aqueous solutions in a static batch system. The kinetic and isothermal parameters of the sorption process were determined. The experimental data were best fitted by a pseudo-second-order model with R2 = 0.994 and χ2 = 0.004. The sorption process of Cr(VI) removal by amino-functionalized sorbent was controlled by both intraparticle diffusion and liquid film diffusion. The equilibrium results showed that the sorption process is best described by the Freundlich model, followed closely by the Sips isotherm model, with a maximum sorption capacity of 64 mg/g. Quantum chemical modeling revealed that the sorption sites on the sorbent surface are fragments with diethylenetriamine and aminopropyl silane groups that coated the magnetic nanoparticles. The calculations showed that Cr(VI) oxyanions (Cr2O72−, CrO42− and HCrO4−) bind to both sorption sites, with diethylenetriamine centers slightly favored. The X-ray photoelectron spectroscopy (XPS) spectra demonstrate that the chromium bound to the sorbent in the form of Cr(III), indicating that the Cr(VI) can be converted on the surface of the sorbent to a less harmful form Cr(III) due to the sorbent’s chemical composition.
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