Molecularly imprinted polymers based on magnetic metal-organic frameworks for surface-assisted laser desorption/ionization time-of-flight mass spectrometry analysis and simultaneous luteolin enrichment

Abstract

UiO-66(NH2), a metal-organic framework, exhibits excellent UV absorption and energy transfer performance and can be used as a substrate for surface-assisted laser desorption/ionization (SALDI) analysis of small molecules. Molecularly imprinted polymers (MIPs) exhibit outstanding selectivity toward certain targets. The complexes of UiO-66(NH2) and MIPs can be applied as both an adsorbent and substrate for SALDI-time-of-flight mass spectrometry (SALDI-TOF MS) analysis of small molecules. Herein, magnetic UiO-66(NH2)-molecularly imprinted polymers (MUMIPs) were prepared for the selective enrichment and detection of luteolin via SALDI-TOF MS. The amino group on UiO-66(NH2) were used as functional monomer to prepare MIPs that interact with luteolin via hydrogen bonding. The surface functional monomer can effectively control the coating thickness of the MIPs to avoid embedding template molecules and enhance adsorption performance. In addition, Fe3O4 particles were introduced for rapid magnetic separation. The physicochemical properties of the MUMIPs were characterized via scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, vibrating sample magnetometry, Brunauer-Emmett-Teller analysis, and X-ray photoelectron spectroscopy. Adsorption experiments and selectivity studies indicated that MUMIPs exhibited good adsorption capacity, fast adsorption rates, and excellent luteolin selectivity. MUMIPs are efficient substrates for the SALDI analysis of luteolin and its structural analogs. In addition, the MUMIPs-SALDI-TOF MS method successfully detected luteolin in rat plasma and urine after administration of oral Chrysanthemum morifolium Ramat extracts. This method possessed high sensitivity with a limit of detection of 0.5 ng/mL. The traditional precipitation method combined with high-performance liquid chromatography-mass spectrometry was also used to analyze luteolin in biological samples. Compared with the traditional method, the novel MUMIP-SALDI-TOF MS method can more effectively detect the target compounds in complex samples. Ultimately, the MUMIP-SALDI-TOF MS method was applied to detect luteolin and its metabolites in rat liver after oral luteolin treatment. Three luteolin metabolites (apigenin, chrysoeriol, and diosmetin) were analyzed using the newly developed MUMIP-SALDI-TOF MS method.