Synthesis of a core-shell magnetic covalent organic framework for the enrichment and detection of aflatoxin in food using HPLC-MS/MS.

A porous magnetic covalent organic framework, Fe3O4@TPBD-TPA (terephthalaldehyde (TPA) , N, N, N', N'-tetrakis(p-aminophenyl)-p-phenylenediamine (TPBD)), was synthesized using the Schiff base reaction under mild reaction conditions. This adsorbent exhibited excellent adsorption performance for aflatoxins. The adsorption capacity of Fe3O4@TPBD-TPA for aflatoxins ranged from 64.4 to 84.4 mg/g. A magnetic solid-phase extraction combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method based on Fe3O4@TPBD-TPA was developed for the efficient determination of four types of aflatoxins in food samples (maize, maize oil, peanut, and peanut oil). The determination coefficients (R2) were ≥0.9972. The method exhibited detection limits ranging from 0.01 to 0.06 µg/kg and spiked recoveries of 80.0 to 113.1%. The intra-day and inter-day precision were less than 6.77%, indicating good repeatability. The adsorbent showed promising prospects for the efficient enrichment of trace amounts of aflatoxins in complex food matrices.

Modeling the distribution of malachite green in zebrafish using matrix-assisted laser desorption/ionization mass spectrometry imaging.

Understanding the spatial distribution of bioactive small molecules is indispensable for elucidating their biological or pharmaceutical roles. Here, a rapid and effective analysis strategy was introduced to study the distribution of veterinary drugs in aquatic products. Malachite green (MG), one of the most widely used veterinary drugs in aquaculture, was selected as the targeted compound. Zebrafish (Danio rerio) was used as a model organism. After an exposure test, the matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) technique was applied to directly analyze the content changes of malachite green in zebrafish tissues. The reliable relationship of exposure time and content change of MG was described precisely by the extended Freundlich equation. The process of modeling was discussed in detail, and some important parameters or trend information was obtained, including the maximum content of MG in different fish tissues, time to maximum content, elimination time, equilibrium content, and so on. With a simplification of sample pretreatment, this research strategy can be used for monitoring the spatial distribution of veterinary drugs and related metabolites of laboratory-exposed fish. The obtained model can provide a perspective for rational drug use in aquaculture and precise drug residue detection in production activities.

[Determination of 22 mycotoxins in milk by liquid chromatography-quadrupole/orbitrap mass spectrometry].

Mycotoxins have carcinogenic, mutagenic, hepatotoxic, nephrotoxic, immunotoxic, neurotoxic, and teratogenic properties. Thus, these substances have attracted significant attention because they pose a threat to human health. As research on mycotoxins deepens, new structural analogues of mycotoxins are constantly being discovered. In this study, a method based on high performance liquid chromatography-quadrupole/orbitrap mass spectrometry was established for the simultaneous determination of 22 mycotoxins in milk. A simple, effective, and rapid pretreatment method was optimized by focusing on the solvent type, extractant volume, and extracting salt based on the characteristics of the mycotoxins and sample matrix. The analytes were extracted using 0.5% formic acid acetonitrile solution and added with sodium chloride to separate fats from water. The samples were centrifuged at 8000 r/min (4 ℃) for 5 min using a centrifuge and then concentrated using nitrogen. The dry residue was dissolved with 50% methanol aqueous solution. Twenty-two mycotoxins were separated on a ZORBAX Eclipse Plus C18 chromatographic column (100 mm×2.1 mm, 1.7 µm), and quantitative analysis was performed using the isotope internal standard method. The analytes were determined by liquid chromatography-quadrupole/orbitrap mass spectrometry in positive electrospray ionization mode. Qualitative analyses of the compounds were performed in full mass spectrometry/data-dependent tandem mass spectrometry (MS/dd-MS2) mode. Good linearities in the range of 0.5-100.0 µg/L were observed for the 22 mycotoxins, and the correlation coefficients (R2) were greater than 0.999. The limits of detection (S/N=3) and quantification (S/N=10) ranged from 0.3 to 0.5 µg/kg and from 1.0 to 1.5 µg/kg, respectively. The average recoveries of the 22 mycotoxins at three spiked levels of 1.5, 5.0, and 15 µg/kg were between 84.7% and 100.8%, with relative standard deviations (RSDs) of 1.2%-9.9%. These findings indicate that the method has high sensitivity and accuracy as well as good precision. Finally, the method was applied to the detection and analysis of mycotoxins in 25 actual commercial milk samples. The results revealed that the selected samples were not contaminated with any of the mycotoxins analyzed. Thus, the proposed method is useful as a quick preprocessing and confirmatory method for the simultaneous determination of mycotoxins in milk.