Profiling fragments for carotenoid esters in Penaeus monodon by ultra-high-performance liquid chromatography/quadrupole-Orbitrap high-resolution mass spectrometry.

RATIONALE: The precise identification of carotenoid esters of Penaeus monodon, especially those in the carotenoid skeleton, needs to occur during mass spectrometry analysis. Detailed structural information about carotenoid esters is significant not only for the assessment of nutritional quality, but also for tracing biosynthetic precursors. METHODS: The profiling of carotenoid esters in P. monodon was elucidated using ultra-high-performance liquid chromatography coupled with quadrupole-Orbitrap high-resolution mass spectrometry (UHPLC/Q-Orbitrap-HRMS). The raw LC/MS data were analyzed using Exact Finder™ software. RESULTS: The structurally relevant ions, *l and *m, were considered markers of the astaxanthin monoester. Moreover, the carotenoid skeleton was unequivocally identified using the diagnostic ions *i, *j/*j' and *g/*g' generated by the carbon-carbon bond cleavage between ß-ionone ketones and conjugated polyene moieties. In total, 24 carotenoid esters were identified in P. monodon based on the fragmentation patterns discussed above. The identified carotenoid skeleton includes astaxanthin, astacene, oxidized astaxanthin and adonixanthin, which have been described for the first time. CONCLUSIONS: Characterization of the unknown carotenoid esters demonstrates the capabilities of this methodology, which is significant for enriching the carotenoid species in P. monodon.

Novel synthesized attapulgite nanoparticles-based hydrophobic monolithic column for in-tube solid-phase microextraction of thiosildenafil, pseudovardenafil, and norneosildenafil in functional foods.

In this study, a novel method which involved in-tube solid-phase microextraction (SPME) using an attapulgite (ATP) nanoparticles-based hydrophobic monolithic column was successfully developed. It was coupled with high-performance liquid chromatography-ultraviolet detection for the determination of three phosphodiesterase-5 (PDE-5) inhibitors, including thiosildenafil, pseudovardenafil, and norneosildenafil, in functional foods. The monolithic column was prepared by one-step polymerization, using 3-trimethoxysilylpropyl methacrylate-modified ATP nanoparticles and 1-butyl-3-vinylimidazolium bromide (VBIMBr) as the functional monomers, and ethylene glycol dimethacrylate (EDMA) as the cross-linker. The obtained poly(ATP-VBIMBr-EDMA) monolith was characterized by scanning electron microscopy equipped with energy-dispersive analysis of X-ray, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. The adsorption capacity, up to 2.00 µg/cm calculated by the Langmuir isotherm model, was about six times that of the poly(VBIMBr-EDMA) monolith. Crucial factors affecting the extraction efficiency, including sample solvent, elution solvent, flow rates of sampling loading and elution, sample loading volume, and elution volume, were investigated in details. Under the optimal in-tube SPME conditions, the proposed method showed good reproducibility with run-to-run, column-to-column, and batch-to-batch relative standard deviations less than 7.2%, and low limits of detection of 0.5-0.9 ng/mL in real samples. Thiosildenafil was detected in four types of functional foods with the contents of 1.30-4.78 µg/g. This newly proposed in-tube SPME method based on poly(ATP-VBIMBr-EDMA) monolith may provide a simple, efficient, and promising alternative to daily monitoring of PDE-5 inhibitors in functional foods.

A novel core-shell up-conversion nanoparticles immunochromatographic assay for the detection of deoxynivalenol in cereals.

Deoxynivalenol (DON) toxin is a type B group of trichothecene mycotoxins mainly originating from specific Fusarium fungi, seriously harming human and livestock health. Herein, a novel core-shell up-conversion nanoparticles immunochromatographic assay (CS-UCNPs-ICA) was developed for deoxynivalenol based on the competitive reaction principle. By exploiting the fluorescence intensity of the T and C lines of CS-UCNPs-ICA, the concentrations of DON were obtained sensitively and precisely under optimized conditions in 5 min with a detection limit of 0.1 ng/mL. The CS-UCNPs-ICA strips only specifically detect DON and its derivatives (3-Ac-DON and 15-Ac-DON), with no cross-reaction with other mycotoxins. The low CV values illustrated a modest intra- and inter-assay variation, confirming the superior precision of this method. In the spiked experiment, the mean recoveries of corn and wheat ranged from 94.74% to 100.90% and 96.21%-104.81%, respectively. Furthermore, the approach generated results that were in good agreement with data from HPLC and ELISA analyses of naturally contaminated feed and cereals, confirming that the significant advantages of proposed strips were their high practicality, rapidness, and simplicity. Therefore, the CS-UCNPs-ICA strips platform serves as a promising candidate for developing new approaches for rapid testing or high throughput screening from DON in food products.

Rapid determination of 93 banned industrial dyes in beverage, fish, cookie using solid-supported liquid-liquid extraction and ultrahigh-performance liquid chromatography quadrupole orbitrap high-resolution mass spectrometry.

Banned industrial dyes are composed of a large number of chemicals with diverse physical and chemical properties, making their simultaneous determination a challenging task. A one-step extraction and purification of 93 banned industrial dyes from beverage, fish and cookie sample methods was proposed by using solid supported liquid-liquid extraction (SLE). The extract was analyzed by ultrahigh-performance liquid chromatography quadrupole orbitrap high-resolution mass spectrometry (UPLC-Q-Orbitrap-HRMS). The quantitative and qualitative mode adopts Q-Orbitrap-HRMS full scan MS (full scan MS1) and data-dependent MS/MS (dd-MS2) acquisition mode. The mass resolution was screened under 70,000 FWHM for full-scan MS1 and 35,000 FWHM for dd-MS2. Linearity was observed in the range of 0.01 âˆ¼ 0.5 µg/mL and the limits of quantification were 0.04 âˆ¼ 0.2 mg/kg for 93 dyes. The average recoveries were 70.5-105.8%, with RSD ≤ 10%. The proposed method has the ability to simultaneously screen many banned dyes in foods with high throughput, sensitivity and reliability.

Hybrid silica material as a mixed-mode sorbent for solid-phase extraction of hydrophobic and hydrophilic illegal additives from food samples.

In the current study, a novel kind of mixed-mode hydrophobic/hydrophilic hybrid silica material has been developed for the solid-phase extraction of hydrophobic and hydrophilic illegal additives from food samples. A hydrophobic hybrid silica material was first prepared by the sol-gel method with tetraethoxysilane, 3-aminopropyltriethoxysilane, and dimethyloctadecyl-[3-(trimethoxysilyl)propyl] ammonium chloride (DTSACl) as precursors. Subsequently, the hydrophobic hybrid silica material was activated by glutaraldehyde, followed by the covalent immobilization of polyethyleneimine (PEI). PEI and the octadecyl group of DTSACl produced the hydrophilic/hydrophobic features of the hybrid silica material. The developed material was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance, zeta potential analyzer, and laser diffraction particle size analyzer, then applied as a hydrophobic and hydrophilic sorbent for the solid-phase extraction (SPE) of benzodiazepines from ginseng amino acid oral liquid as well as melamine and cyromazine from powdered milk, followed by RPLC/HILIC-MS/MS analysis. The composition and volumes for SPE loading and elution solutions were optimized in detail. Coupled with RPLC/HILIC-MS/MS, the proposed method provided satisfactory linearity in the range from 0.9-3.2 µg kg-1 to 100-250 µg kg-1 with the coefficients of determination higher than 0.99. The limits of detection ranged from 0.3 to 1.0 µg kg-1, and the recoveries ranged from 81.1% to 109.0% with the relative standard deviations less than 8.5% (n = 3). This report offers a new mixed-mode hydrophobic/hydrophilic hybrid silica material to extract trace hydrophobic and hydrophilic additives from complex samples.