Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples.

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4'-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214-327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

MOF-derived porous carbon microspheres Ni@C-acid as solid-phase microextraction coating for extraction of polycyclic aromatic hydrocarbons from tea infusions.

The improvement of the stability and adsorption properties of materials on targets in sample pre-treatment has long been an objective. Extensive efforts have been made to achieve this goal. In this work, metal-organic framework Ni-MOF precursors were first synthesized by solvothermal method using polyvinylpyrrolidone (PVP) as an ideal templating agent, stabiliser and nanoparticle dispersant. After carbonization and acid washing, the nanoporous carbon microspheres material (Ni@C-acid) was obtained. Compared with the material without acid treatment (Ni@C), the specific surface area, pore volume, adsorption performance of Ni@C-acid were increased. Thanks to its excellent characteristics (high stability, abundant benzene rings), Ni@C-acid was used as fiber coatings in headspace solid-phase microextraction (HS-SPME) technology for extraction and preconcentration of polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The experimental parameters of extraction temperature, extraction time, agitation speed, desorption temperature, desorption time and sodium chloride (NaCl) concentration were studied. Under optimal experimental conditions, the wide linear range (0.01-30 ng mL-1), the good correlation coefficient (0.9916-0.9984), the low detection limit (0.003-0.011 ng mL-1), and the high enrichment factor (5273-13793) were obtained. The established method was successfully used for the detection of trace PAHs in actual tea infusions samples and satisfied recoveries ranging from 80.94-118.62 % were achieved. The present work provides a simple method for the preparation of highly stable and adsorbable porous carbon microsphere materials with potential applications in the extraction of environmental pollutants.

Confinement effect of ionic liquid: Improve of the extraction performance of parent metal organic framework for phthalates.

In order to better identify the hazards of pollutants, developing the analytical methods that can sensitively detect and precisely monitor the content of trace pollutants has been the constant pursuit. In this paper, a new solid phase microextraction coating-ionic liquid/metal organic framework (IL/MOF) was obtained through the IL-induced strategy and used for the solid phase microextraction (SPME) process. IL was introduced into metal-organic framework (MOF) cage based on the anion of ionic liquid could interact strongly with the zirconium nodes of UiO-66-NH2. The introduction of IL not only increased the stability of composite, the hydrophobicity of IL also changed the environment of MOF channel, providing the hydrophobic effect to the targets. The confinement effect of IL effectively improved the extraction performance of parent MOF and the extraction performance of synthesized IL/UiO-66-NH2 for phthalates (PAEs) were 1.3-3.0 times that of parent UiO-66-NH2. Thanks to the strong interaction force (hydrogen bonding interaction, π-π stacking, hydrophobic interaction force), the IL/UiO-66-NH2-coated fiber coupled with gas chromatography-mass spectrometer showed a wide linear ranges (1-5000 ng L-1) with good correlation (R2, 0.9855-0.9987), lower detection limit (0.2-0.4 ng L-1) and satisfactory recoveries (95.3-119.3%) for PAEs. This article is dedicated to provide another way to improve the extraction performance of material.