Flowerlike Ni-NiO composite as magnetic solid-phase extraction sorbent for analysis of carbendazim and thiabendazole in edible vegetable oils by liquid chromatography-mass spectrometry.

A rapid, selective, and sensitive method was developed for the detection of carbendazim and thiabendazole in edible vegetable oil. Two benzimidazole analytes were pre-concentrated by magnetic solid phase extraction (MSPE) using flowerlike Ni-NiO composite as sorbents and followed by LC-MS/MS analysis. The flowerlike Ni-NiO composite sorbent displayed a high affinity towards benzimidazole analytes due to the reversible coordination interaction between the Ni(Ⅱ) ion and the electron-donating imidazole group. In comparison to the previous methods, this procedure is less time-consuming and simpler during sample preparation. The parameters affecting the extraction efficiency were optimized in detail. The method was validated according to SANTE/12682/2019. The limits of detection were in the range of 0.001-0.003 mg•kg-1. The recoveries ranged from 89.3% to 110.7% with inter-day and inter-day precision less than 10.9%. The results indicate that flowerlike Ni-NiO composite might be a promising alternative for MSPE of benzimidazole compounds in foods.

Use of Pollen Solid-Phase Extraction for the Determination of trans-Resveratrol in Peanut Oils.

In this study, a simple and convenient method for the determination of trans-resveratrol (TRA) in peanut oils based on pollen grain solid-phase extraction (SPE) was developed. Pollen grains were used as normal-phase SPE sorbent to separate TRA from peanut oils for the first time. As a naturally occurring material, pollen grains exhibited an excellent adsorption capacity for polyphenolic compounds due to their particular functional structures such as hydroxyl groups, saturated and unsaturated aliphatic chains with aromatics. Their stable compositions as well as adequate particle size (30-40 µm) also make them suitable for SPE. Several parameters influencing extraction performance were investigated. Coupled with high-performance liquid chromatography-ultraviolet detection (HPLC-UV), a green purification method for fast determination of TRA in peanut oils using pollen grain cartridges as sorbents was established. The linearity range of the proposed method was 10-2500 ng · g(-1) with a satisfactory correlation coefficient (r(2)) of 0.9999. The limit of detection (LOD) for TRA in peanut oils was 2.7 ng · g(-1), and the recoveries in spiked oil samples were from 70.2% to 98.4% with the relative standard deviations (RSDs) less than 4.9% (intraday) and 5.2% (interday). This method was successfully applied to the analysis of TRA in several peanut oils with different brands from local market as well as other kinds of vegetable oils.

Using pollen grains as novel hydrophilic solid-phase extraction sorbents for the simultaneous determination of 16 plant growth regulators.

In this article, pollen grains were for the first time used as a hydrophilic solid-phase extraction (HILIC-SPE) sorbent for the determination of 16 plant growth regulators (PGRs) in fruits and vegetables. Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM) and nitrogen sorption porosimetry (NSP) were used to investigate the chemical structure and the surface properties of the pollen grains. Pollen grains exhibited an excellent adsorption capacity for some polar compounds due to their particular functional groups. Several parameters influencing extraction performance were investigated. A green and simple HILIC-SPE-method using pollen grain cartridge for purification of fruit and vegetable extractions, followed by ultra-high performance liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-MS/MS) was established. Good linear relationships were obtained for 16 PGRs with correlation coefficients (R) above 0.9980. The limits of detection (LODs) of 16 PGRs in cucumber were in the range of 0.01-1.10 µg · kg(-1). Reproducibility of the method was evaluated by intra-day and inter-day precisions with relative standard deviations (RSDs), which were less than 14.4%. We successfully applied this methodology to analyze 16 PGRs in 8 different kinds of fruits and vegetables. The recoveries from samples spiked with 16 PGRs were from 80.5% to 119.2%, with relative standard deviations less than 15.0%.

Sequential enrichment with titania-coated magnetic mesoporous hollow silica microspheres and zirconium arsenate-modified magnetic nanoparticles for the study of phosphoproteome of HL60 cells.

As one of the most important types of post-translational modifications, reversible phosphorylation of proteins plays crucial roles in a large number of biological processes. However, owing to the relatively low abundance and dynamic nature of phosphorylation and the presence of the unphosphorylated peptides in large excess, phosphopeptide enrichment is indispensable in large-scale phosphoproteomic analysis. Metal oxides including titanium dioxide have become prominent affinity materials to enrich phosphopeptides prior to their analysis using liquid chromatography-mass spectrometry (LC-MS). In the current study, we established a novel strategy, which encompassed strong cation exchange chromatography, sequential enrichment of phosphopeptides using titania-coated magnetic mesoporous hollow silica microspheres (TiO2/MHMSS) and zirconium arsenate-modified magnetic nanoparticles (ZrAs-Fe3O4@SiO2), and LC-MS/MS analysis, for the proteome-wide identification of phosphosites of proteins in HL60 cells. In total, we were able to identify 11,579 unique phosphorylation sites in 3432 unique proteins. Additionally, our results suggested that TiO2/MHMSS and ZrAs-Fe3O4@SiO2 are complementary in phosphopeptide enrichment, where the two types of materials displayed preferential binding of peptides carrying multiple and single phosphorylation sites, respectively.

Dispersive microextraction based on "magnetic water" coupled to gas chromatography/mass spectrometry for the fast determination of organophosphorus pesticides in cold-pressed vegetable oils.

This article presents a novel application of dispersive microextraction based on "magnetic water" (m-water) for the purification of organophosphorus pesticides (methamidophos, omethoate, monocrotophos) from cold-pressed vegetable oils. In the present study, a trace amount of water (extractant) was adsorbed on bare Fe3O4 by hydrophilic interaction to form m-water. Rapid extraction can be achieved while the m-water is dispersed in the sample solution with the aid of a vigorous vortex. After extraction, the analyte-adsorbed m-water can be readily isolated from the sample solution by a magnet, which could greatly simplify the operation and reduce the whole pretreatment time. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for pesticide analysis was established by coupling with gas chromatography/mass spectrometry (GC/MS). The linearity range of the proposed method was 2-100 ng/g with satisfactory correlation coefficients (R) of 0.9997-0.9998, and the limits of quantification (LOQ) for the target compounds were in the range of 0.70-1.27 ng/g. In addition, the reproducibility was obtained by evaluating the intra- and interday precisions with relative standard deviations (RSDs) less than 7.2% and 6.5%, respectively. Finally, the established "magnetic water" microextraction method was successfully applied for the determination of pesticide residues in several kinds of cold-pressed vegetable oils.

Humic acid-bonded silica as a novel sorbent for solid-phase extraction of benzo[a]pyrene in edible oils.

A novel solid-phase extraction (SPE) sorbent, humic acid-bonded silica (HAS), was prepared. Humic acids (HAs) were grafted onto silica matrices via an amide linkage between humyl chloride and the amido terminus of 3-aminopropyltrimethoxysilane (APTS)-silica gel. The resulting material was characterized by Fourier transform infrared spectrometer, elemental analysis, and nitrogen adsorption analysis. This sorbent exhibits an excellent adsorption capacity for some electron-abundant analytes owing to its peculiar structure. In this paper, we choose benzo[a]pyrene (BaP) in oil as a probe to validate the adsorption capacity of the material. Thus a fast, cheap and simple SPE method with humic acid-bonded silica cartridge for edible oil clean-up, followed by high-performance liquid chromatography (HPLC) with fluorescence detection was established. The effects of experimental variables, such as washing and elution solvents, and the amount of sorbents have been studied. The recoveries of BaP in edible oils spiked at 0.2-100 microg kg(-1) were in the range of 78.8-102.7% with relative standard deviations ranging between 1.3 and 9.3%; the limit of detection was -0.06 microg kg(-1).

[Isolation and purification of the process impurity in losartan by reversed-phase column chromatography].

A process impurity (approximately 4%, w/w) was isolated from losartan crude by low-pressure reversed-phase column chromatography. At first the elution portions containing the target compound were collected. After evaporation and recrystallization, the purity of the target compound was found to be over 99% based on high performance liquid chromatography with ultraviolet absorption. The electrospray ionization-mass spectrometry result showed that it was an isomeric compound of losartan, which had same fragmentation pattern with its parent compound. And at last the compound was further characterized by nuclear magnetic resonance. This research demonstrates that the low-pressure reversed-phase column chromatography can raise separation efficiency and recovery comparing with other conventional column chromatography, and the technique can be applied as an effective means for the enrichment and extraction of impurities in pharmaceutical separation.