Synthesis of spindle-like amino-modified Zn/Fe bimetallic metal-organic frameworks as sorbents for dispersive solid-phase extraction and preconcentration of phytohormoes in vegetable samples

Amino-modified Zn/Fe bimetallic metal-organic frameworks (NH2-Zn/Fe-MIL-88) were synthesized using a one-step solvothermal method with FeCl3·6H2O and Zn(NO3)2·6H2O as metal salts and 2-aminoterephthalic acid as organic ligand. The morphology of NH2-Zn/Fe-MIL-88 can be regulated from octahedral-like to spindle-like with changing molar ratios of metal salts. Using NH2-Zn/Fe-MIL-88 as sorbent, a dispersive solid-phase extraction with putting sorbents into sample solution to extract targets was developed to preconcentrate phytohormones in vegetables. To study the extraction efficiency, a series of NH2-Zn/Fe-MIL-88s with varying molar ratios of metal salts were prepared. The results indicated that NH2-Zn/Fe-MIL-88(1) presented the highest extraction efficiency (82.6 %-98.1 %) to phytohormones among all prepared NH2-Zn/Fe-MIL-88(x). The limits of detection were calculated at 0.07-0.15 ng/mL. The adsorption isotherms and kinetic parameters of NH2-Zn/Fe-MIL-88 for phytohormones were conformed to Langmuir and pseudo-second-order models. The NH2-Zn/Fe-MIL-88 as sorbent combined with HPLC was applied to detect phytohormones in cucumber and tomato samples.