Ultra-High Adsorption Capacity of Core-Shell-Derived Magnetic Zeolite Imidazolate Framework-67 as Adsorbent for...

A core-shell-derived structural magnetic zeolite imidazolate framework-67 (Fe₃O₄-COOH@ZIF-67) nanocomposite was fabricated through a single-step coating of zeolite imidazolate framework-67 on glutaric anhydride-functionalized Fe₃O₄ nanosphere for the magnetic solid-phase extraction (MSPE) of theophylline (TP). The Fe₃O₄-COOH@ZIF-67 nanocomposite was characterized through scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, Zeta potential analysis, X-ray diffraction, Brunauer-Emmett-Teller, and vibrating sample magnetometer. The material has a high specific surface area and good magnetism, which maintains the regular dodecahedron structure of ZIF-67 without being destroyed by the addition of Fe₃O₄-COOH nanospheres. The Fe₃O₄-COOH@ZIF-67 can rapidly adsorb TP mainly through the strong coordination interaction between undercoordinated Co²⁺ on ZIF-67 and -NH from imidazole of TP. The adsorption and desorption conditions, such as the amount of adsorbent, adsorption time, pH value, and elution solvent, were optimized. The kinetics of TP adsorption on Fe₃O₄-COOH@ZIF-67 was found to follow pseudo-second-order kinetics. The Langmuir model fits the adsorption data well and the maximum adsorption capacity is 1764 mg/g. Finally, the developed MSPE-HPLC method was applied in the enrichment and analysis of TP in four tea samples and rabbit plasma. TP was not detected in oolong tea and rabbit plasma, and its contents in jasmine tea, black tea, and green tea are 5.80, 4.31, and 1.53 μg/g, respectively. The recoveries of spiked samples are between 74.41% and 86.07% with RSD in the range of 0.81-3.83%. The adsorption performance of Fe₃O₄-COOH@ZIF-67 nanocomposite was nearly unchanged after being stored at room temperature for at least 80 days and two consecutive adsorption-desorption cycles. The results demonstrate that Fe₃O₄-COOH@ZIF-67 nanocomposite is a promising magnetic adsorbent for the preconcentration of TP in complex samples.