Exploration of porous imine-based covalent organic framework for solid-phase extraction of five trace sulfonamides in food samples.

In this article, a highly crystalline porous imine-based covalent organic framework was synthesized at room temperature and used as solid-phase extraction (SPE) adsorbent for the purification and enrichment of trace sulfonamides (SAs) from food samples. The structure of the obtained material was characterized and studied in detail. The extraction process was optimized and the final elution was determined by the ultra-high-performance liquid chromatography-quadrupole time of flight mass spectrometry method. Low limits of detection (0.02-0.19 µg/kg) were obtained under optimal conditions, with the recoveries ranging from 70.5% to 105.3% when spiked at different levels. The adsorption process of the material for SAs was fitted by the Langmuir and Freundlich adsorption isotherm model, and the extraction capacity for Nitrofuran metabolites from food samples was also investigated for comparison. The results demonstrated that the framework was a good candidate SPE adsorbent that can be used for the enrichment of drug residues in complex matrix, and the work may provide a systematic study method for the development of porous adsorbents.

Facile synthesis of triazine-based porous organic polymer for the extraction and determination of nitrofuran metabolites residues from meat samples with ultra-high performance liquid chromatography-quadrupole time of flight mass spectrometry.

In this work, a novel triazine-based porous organic polymers, TAPT-BPDD, was firstly synthesized by a facile method at room temperature. After characterized by FT-IR, FE-SEM, XRPD, TGA, and nitrogen-sorption experiments, TAPT-BPDD was applied as solid-phase extraction (SPE) adsorbent for the extraction of four trace nitrofuran metabolites (NFMs) from meat samples. The key parameters including the adsorbent dosage, sample pH, type and volume of eluents, type of washing solvents were evaluated in the extraction process. Combined with ultra-high performance liquid chromatography-quadrupole time of flight mass spectrometry (UHPLC-QTOF-MS/MS) analysis, good linear relationship (1-50 µg·kg-1, R2>0.9925) and low limits of detection (LODs, 0.05-0.56 µg·kg-1) were obtained under the optimal conditions. When spiked at different level, the recoveries were in the range of 72.7-111.6%. The adsorption isothermal model and extraction selectivity of TAPT-BPDD were also studied in detail. The results showed that TAPT-BPDD was a kind of promising SPE adsorbent for the enrichment of organics in food samples.

Exploration of an imine-based covalent organic framework for the solid phase extraction of nitroimidazoles in milk and meat samples.

TAPT-AN-COF, an imine-based covalent organic framework, was synthesized by a solvothermal method of 2,4,6-trihydroxy-benzene-1,3,5-tricarbaldehyde (TP) and 4,4',4″-(1,3,5-Triazine-2,4,6-triyl)trianiline (TAPT). The structure was characterized and tested by several techniques, revealing that the material had good stability and high specific surface area. The adsorption experiment demonstrates that the adsorption isotherm of TAPT-AN-COF followed the Freundlich isothermal equation, while its adsorption kinetics conformed to the pseudo second-order kinetic model. After characterization, the prepared TAPT-AN-COF was used to separate and enrich nitroimidazoles (NDZs) in milk and meat as the solid-phase extraction (SPE) adsorbent. The effects of adsorbent dosage, pH value, washing solvent, elution solvent type and volume on recoveries were studied. Under the optimal conditions, a method for the determination of NDZs in milk and meat samples was established based on high performance liquid chromatography-ultraviolet detection(HPLC-UVD).The result showed that NDZs had good linearity in the concentration range of 25-500 µg·kg-1, and the determination coefficients (r2) were all above 0.99. When spiked at 25, 50 and 125 µg·kg-1, the recoveries of three kinds of food samples ranged from 64.5% to 85.3%, the limits of detection (LODs) were between 2 and 10 µg·kg-1, and the relative standard deviations were all below 15.9%. In addition, the recoveries of NDZs didn't decrease significantly after being reused for 6 times, showing that TAPT-AN-COF has excellent reusability. Compared with HLB and MCX sorbents, TAPT-AN-COF had better extraction efficiency and qualified purification efficiency. The established method had a satisfying performance on the determination of NDZs in food samples.

Evaluation of a porous imine-based covalent organic framework for solid-phase extraction of nitroimidazoles.

Covalent organic framework materials (COFs), a kind of porous organic material, have excellent potential application in the field of sample pretreatment due to their high surface areas and thermal stability. In this work, a porous imine-based COF, named BP-COF, was fabricated by a solvothermal method using 2,2'-bipyridine-5,5'-dicarboxaldehyde and 1,3,5-tris(4-aminophenyl) benzene as monomers. After a series of structural characterization studies, the BP-COF was used as a solid-phase extraction (SPE) adsorbent for the extraction and enrichment of nitroimidazoles and their metabolites. Several parameters were investigated during the extraction process, including the sorbent dosage, loading pH value, the washing and elution solvent, and the breakthrough volume. By coupling with UPLC-QTOF-MS/MS, a sensitive and facile method was established for the quantitation analysis of NDZs. Under the optimum conditions, a low detection limit (0.015-0.12 ng mL-1) and wide linearity (0.2-500 ng mL-1) with higher R2 were obtained. In addition, the developed method was applied for the determination of NDZs in four water samples with recoveries in the range of 71.7-115.9% and RSDs less than 8.3%. The results indicated that the BP-COF shows great potential for the enrichment of NDZs in water samples.

Tryptophan and kynurenine stimulate human decidualization via activating Aryl hydrocarbon receptor: Short title: Kynurenine action on human decidualization.

Decidualization is essential for successful pregnancy in rodents and primates. Although L-Tryptophan and its metabolites are essential for mammalian pregnancy, the underlying mechanism is poorly defined. We explored effects of tryptophan and kynurenine on human in vitro decidualization in human endometrial stromal cell line and primary endometrial stromal cells. Tryptophan significantly stimulates the expression of prolactin and insulin growth factor binding protein 1, reliable markers for human decidualization. When stromal cells are treated with tryptophan, tryptophan hydroxylase-1 remains unchanged, but indoleamine 2,3-dioxygenase 1 is significantly increased, suggesting tryptophan is mainly metabolized through kynurenine pathway. Kynurenine significantly stimulates insulin growth factor binding protein 1 expression. Aryl hydrocarbon receptor and its target genes (P450 1A1 and P450 1B1) are significantly increased by tryptophan and kynurenine. The induction of tryptophan and kynurenine on insulin growth factor binding protein 1 is abrogated by CH223191, an aryl hydrocarbon receptor inhibitor. Cytochrome P450 1A1 and P450 1B1 catalyze the oxidative metabolism of estradiol to catechol estrogens (2-hydroxy estradiol and 4-hydroxy estradiol), respectively. Insulin growth factor binding protein 1 is up-regulated by 2-hydroxy estradiol and 4-hydroxy estradiol. Interferon-γ significantly induces the expression of indoleamine 2,3-dioxygenase 1, aryl hydrocarbon receptor and insulin growth factor binding protein 1. All the data are also verified in primary human stromal cells. Our data indicate that Interferon-γ-induced kynurenine pathway promotes human decidualization via aryl hydrocarbon receptor signaling.

The fabrication of a covalent triazine-based organic framework for the solid-phase extraction of fourteen kinds of sulfonamides from meat samples.

A novel covalent triazine-based organic framework (CTF), SCAU-2, was fabricated and used as an adsorbent for the solid-phase extraction of fourteen kinds of sulfonamides (SAs) from meat. Another CTF, SCAU-1, was adopted as a comparison material, as it has a similar motif. A series of structural characterization steps was carried out on the synthesized materials and several parameters were investigated during the extraction process, including the amount of adsorbent, the dilution ratio, the pH of the sample, and the washing and elution solvents. After detection with UHPLC-Q/TOF-MS/MS, the results revealed that SCAU-2 showed high extraction efficiencies towards the selected SAs. The LOD values are from 0.05 to 0.54 ng g-1, and the recoveries are from 84.1% to 91.9%, with RSDs ranging from 3.2% to 4.8% for SCAU-2 when spiked at 50 ng g-1. The results demonstrated that the proposed method has good applicability for the determination of SAs in complicated samples.