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

Abstract

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.

Keywords: 1-Naphthylacetic acid (PubChem CID 6862); 2-Naphthylacetic acid (PubChem CID 11393); 6-Benzylaminopurine (PubChem CID 62389); Abscisic acid (PubChem CID 5375199); Bimetallic metal-organic framework; Dispersive solid-phase extraction; Indole-3-acetic acid (PubChem CID 802); Indole-3-butyric acid (PubChem CID 8617); NH(2)-Zn/Fe-MIL-88; Phytohormones; Zn/Fe bimetal-organic framework.