A Zr(IV)-based porphyrinic metal-organic framework as a solid-phase sorbent for extraction of sulfonamides prior to their quantitation by LC-MS.

A porphyrinic metal-organic framework (PCN-224) was fabricated and used as an adsorbent for solid-phase extraction of ultratrace levels of polar sulfonamide antibiotics from food and drinking waters. The PCN-224 was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and powder X-ray diffraction analyses. Parameters affecting the extraction efficiency were optimized. The sulfonamides were quantified by liquid chromatography-tandem mass spectrometry. Figures of merit include (a) low limits of detection (0.07-0.47 ng·L-1), (b) wide linear ranges (0.5-2000 ng·L-1), and (c) good repeatabilities (2.8%-6.7%) and reproducibilities (1.7%-5.1%). The method was successfully applied to the determination of sulfonamides in food and drinking water samples. Graphical abstract A Zr(IV)-based porphyrinic metal-organic framework (PCN-224) was synthesized from a Zr6 cluster and the H2TCPP ligand. It was used for solid-phase extraction of sulfonamides from food and drinking water samples coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for determination.

Highly Stable Zr(IV)-Based Porphyrinic Metal-Organic Frameworks as an Adsorbent for the Effective Removal of Gatifloxacin from Aqueous Solution.

Water stable Zr-metal−organic framework nanoparticles (PCN-224 NPs, PCN refers to porous coordination network) have been solvothermally synthesized. PCN-224 NPs show spherical shape with smooth surface and particle size of approximately 200 nm. PCN-224 NPs can be stable in acid and aqueous solutions, as confirmed by powder X-ray diffraction. Gatifloxacin (GTF) adsorption measurements showed that PCN-224 NPs exhibit a high adsorption capacity of 876 mg·g−1. Meanwhile, the adsorption factors, adsorption characteristics, and mechanisms of GTF were investigated in batch adsorption experiments.

Cationic covalent organic nanosheets for rapid and effective detection of phenoxy carboxylic acid herbicides residue emitted from water and rice samples.

Development of efficient and sensitive adsorbent for capturing phenoxy carboxylic acids (PCAs) from environmental and food samples is necessary because PCAs could threaten human health. Designing nanoparticle with multiple functional groups is beneficial to achieve the strong adsorption interaction and the specific recognition for target compound. In this paper, TpTGCl as an ionic covalent organic framework (ICOF), that could offer plenty of positive charges and hydrogen-bonding sites, was fabricated. TpTGCl achieved quicker, more sensitive enrichment for anionic PCAs. The analysis of binding affinity by density functional theory (DFT) demonstrated that PCAs bonded to TpTGCl primarily via electrostatic attraction, N  H···O and O  H···O, and C  H···π interaction. The quantitative approach indicated low limits of detection (0.016-0.036 ng·g-1 for rice and 0.43-0.78 ng·L-1 for water). Furthermore, successfully determining PCAs emitted from real samples indicated the applicability of TpTGCl.

High crystalline magnetic covalent organic framework with three-dimensional grapevine structure for ultrasensitive extraction of nitro-polycyclic aromatic hydrocarbons in food and environmental samples.

Developing and establishing an efficient pre-treatment approach for the precise extraction of nitrated-polycyclic aromatic hydrocarbons (N-PAHs) from real-life samples is critical for ensuring their safety. In this study, a novel crystalline magnetic covalent organic framework with a grapevine structure not a single core-shell, Fe3O4@TAPT-DMTA-COF, was fabricated via chemical bonding. Unchanging the reticulated structure and high crystallinity of TAPT-DMTA-COF, the combination made this material possess not only simple operation via magnetic decantation but also remarkable chemical stability. Fe3O4@TAPT-DMTA-COF had a large surface area (1578.45 m2/g), and rich electronegative triazine-groups, which makes it become a superior magnetic enrichment material for trace N-PAHs. For N-PAHs analysis, low limits of detection (LODs) (1.43-17.24 ng/L), excellent relative standard deviations (RSDs ≤ 11.52%), and wide linearity (10-5000 ng/L) were obtained. Real-life applications based on this composite have been successfully explored by capturing the N-PAHs emitted from food and environmental samples.

Triazine-cored covalent organic framework for ultrasensitive detection of polybrominated diphenyl ethers from real samples: Experimental and DFT study.

Food and environmental safety issues attributable to the polybrominated diphenyl ethers (PBDEs) are gaining increasing attention, and these urge us to establish a high-performance sample-handling technique. In this study, an outstanding adsorption performance with short adsorption time (10 min) was achieved for PBDEs using a novel synthesized dispersive solid-phase extraction adsorbent, a reticulated covalent organic framework with N/O functional groups (i.e., imine linkage, triazine, and methoxy) (TAPT-DMTA-COF). By conducting sufficient experimentation and theoretical simulation on adsorption mechanism, the halogen bond between electronegative N/O atoms of TAPT-DMTA-COF and the electropositive Br atoms of PBDEs were observed to play a more pivotal role than π-π, C-H…π interactions, and hydrophobic effects. Furthermore, the positive linear relation between calculated adsorption energy and Br content directly clarified that enrichment behavior of PBDEs can be attributed to halogen bonding. These data implied that integrated nanostructure (i.e., N/O functional groups and reticulated architecture) effectively enhanced adsorption capacity. In case of PBDE analysis, this approach achieved excellent results with low limits of detection (0.03-0.13 ng L-1). Finally, the promising potential applications of aforementioned method were verified by spiking water, fish, and milk samples with PBDEs; good PBDEs recoveries were obtained.