Comparative Analysis of Polyphenols in Lycium barbarum Fruits Using UPLC-IM-QTOF-MS.

Variety, geographical origin, and harvest season are important factors affecting the accumulation of polyphenols in Lycium barbarum. In this study, the effects of these factors on the polyphenolic components of this species were analyzed using ultra-performance liquid chromatography ion mobility quadrupole time-of-flight mass spectrometry. Moreover, the in vitro antioxidant activities of fruit extracts from this species were evaluated. The total polyphenolic contents of L. barbarum fruits from Jinghe County in Xinjiang and Zhongning County in Ningxia were 5.52-11.72 and 7.06-9.37 mg (gallic acid equivalent)/g dry weight, while the total flavonoid contents of L. barbarum fruits from these regions were 12.52-30.29 and 12.67-20.77 mg (rutin equivalent)/g dry weight, respectively. Overall, 39 types of polyphenols were identified in the fruit extracts, including 26 flavonoids, 10 phenolic acids, and three tannins. Of these, 11 polyphenols were quantitatively analyzed, which revealed rutin to be the most dominant polyphenolic component in fruits from Jinghe and Zhongning. There were significant differences (p < 0.05) in the polyphenolic contents and antioxidant activities of L. barbarum fruit extracts, depending on the geographical origin, variety, and harvest season. The antioxidant activity of this species was found to be significantly positively correlated with the polyphenolic contents. This study provided scientific guidance for comprehensive applications of polyphenols from different varieties of L. barbarum from separate geographical origins.

Multiresidue Determination of 26 Quinolones in Poultry Feathers Using UPLC-MS/MS and Their Application in Residue Monitoring.

As a non-traditional sample matrix, feather samples can be used to effectively monitor antibiotic addition and organismal residue levels in poultry feeding. Therefore, an ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed to simultaneously determine the residue levels of 26 quinolones in poultry feathers. The feather samples were extracted by sonication with a 1% formic acid and acetonitrile mixture in a water bath at 50 °C for 30 min, purified by the adsorption of multiple matrix impurities, dried with nitrogen, redissolved, and analyzed by UPLC-MS/MS. The linearity, limit of detection (LOD), limit of quantification (LOQ), recovery and precision were calculated. The 26 antibiotics demonstrated good linearity in the linear range. The recoveries and coefficients of variation were 78.9-110% and <13.7% at standard spiked levels of 10, 100 and 200 µg/kg, respectively. The LOD and LOQ were 0.12-1.31 and 0.96-2.60 µg/kg, respectively. The method also successfully identified quinolone residues in 50 poultry feather samples. The results showed that quinolones can accumulate and stabilize for a certain period of time after transferring from the body to the feathers of poultry.

Pesticide Residue Behavior and Risk Assessment in Celery after Se Nanoparticles Application.

This study investigates pesticide levels in celery, and compares their degradation, dissipation, distribution, and dietary risk after spraying with selenium (Se) nanoparticles. Abamectin, imidacloprid, acetamiprid, thiamethoxam, and lambda-cyhalothrin were sprayed at 1.6, 6.8, 2.0, 1.0, and 0.7 g a.i. ha-1 followed by a 2 g·ha-1 Se nanoparticle application during the growing period. Thiamethoxam, abamectin, imidacloprid, lambda-cyhalothrin, and acetamiprid in celery degraded following a first order kinetic model after 2 g·ha-1 Se nanoparticles application. With the exception of acetamiprid, the half-lives of thiamethoxam, abamectin, imidacloprid, and lambda-cyhalothrin were reduced from 2.4, 0.5, 1.2, 4.2 days without Se nanoparticles application to 1.4, 0.2, 0.9, 3.7 days with the addition of Se nanoparticles (2 g·ha-1), respectively. The chronic dietary exposure risk probability (RQc) and the acute dietary exposure risk probability (RQa) of celery after Se nanoparticles application were within acceptable limits for consumption except for abamectin.

A QuEChERS-Based Liquid Chromatography-Tandem Mass Spectrometry Method for the Simultaneous Determination of Nine Zearalenone-Like Mycotoxins in Pigs.

The determination of zearalenone (ZEN) and its derivatives as biomarkers in animal tissues or organs plays an important role in mycotoxin monitoring and can promote effective exposure assessment. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous quantification of nine ZEN-like mycotoxins, including three glucuronides in different pig tissues (heart, liver, spleen and muscle) was developed and validated in this study. Tissue samples were extracted using a quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction and clean-up procedure, and analyzed by LC-MS/MS in multiple reaction monitoring (MRM) mode. Dynamic linear ranges for each target analyte were determined with R² between 0.916 and 0.999. The LODs of the six ZENs were achieved in the range of 0.5-1 ng/g and the LOQs varied from 1 ng/g to 2 ng/g. The satisfying intra-day and inter-day reproducibility (both RSDr and RSDR < 20%) indicated a good stability of this method. The recoveries of the nine target analytes were in the range of 70-110%. The validation results showed that this LC-MS/MS method coupled with QuEChERS sample pretreatment is effective and suitable for the simultaneous quantitation of ZEN metabolites in pigs. It has been applied to analysis of the pig tissues in this research and can be also adapted for samples in the mycotoxin research field.

Acaricidal Activity and Synergistic Effect of Thyme Oil Constituents against Carmine Spider Mite (Tetranychus Cinnabarinus (Boisduval)).

Studies examining the use of essential oils as replacements for synthetic insecticides require an understanding of the contribution of each constituent present, interactions among these components, and how they relate to overall toxicity. In the present study, the chemical composition of commercial thyme oil was identified by gas chromatography-mass spectrometry. Thyme oil and blends of its major constituents were tested for their acaricidal activitities against carmine spider mites (Tetranychus cinnabarinus (Boisduval)) using a slide-dip bioassay. Natural thyme oil showed greater toxicity than any single constituent or blend of constituents. Thymol was the most abundant component (34.4%), and also possessed the strongest acaricidal activity compared with other single constituents. When tested individually, four constituents (linalool, terpinene, p-cymene and carvacrol) also had activity, while α-pinene, benzoic acid and ethyl gallate had almost no activity. The toxicity of blends of selected constituents indicated a synergistic effect among the putatively active and inactive constituents, with the presence of all constituents necessary to reach the highest toxicity. The results indicated that thyme oil and some of its major constituents have the potential to be developed into botanical acaricides.

Metabolic Profiling on Alternaria Toxins and Components of Xinjiang Jujubes Incubated with Pathogenic Alternaria alternata and Alternaria tenuissima via Orbitrap High-Resolution Mass Spectrometry.

Xinjiang jujubes (Zizyphus rhamnaceae) are important agro-economical foods with the highest planting area and yields in China; however, black spot disease and contaminated Alternaria toxins have unfortunately caused a decline or loss of jujube nutritional quality in recent years. In this study, we used ultrahigh-performance liquid chromatography coupled to Orbitrap high-resolution mass spectrometry to profile both Alternaria toxins and components in three representative Xinjiang jujubes, Hami Huang, Hetian Jun, and Ruoqiang Hui. Before liquid chromatography-mass spectrometry analysis, jujubes were inoculated with two main pathogens of Alternaria alternata (Aa) and Alternaria tenuissima (At). Different combinations of jujube varieties with pathogenic isolates display different metabolic profiles, as expected. Moreover, four major Alternaria toxins, alternariol, alternariol monomethyl ether, altenuene, and tenuazonic acid, were detected in all samples. The inoculation of both pathogens significantly decreased the levels of nutrients and metabolites in jujube, including four saponins, three organic acids, and three alkaloids, whereas it increased the level of several glycerol phosphates. The flavonoid profiles are diverse. Lastly, inoculation of Aa changes more metabolites in jujubes than At. Our data provide insights to better understand the detrimental contamination of Alternaria pathogens in Xinjiang jujubes and improve food safety of jujubes.

The reference dose for subchronic exposure of pigs to cadmium leading to early renal damage by benchmark dose method.

Pigs were exposed to cadmium (Cd) (in the form of CdCl(2)) concentrations ranging from 0 to 32mg Cd/kg feed for 100 days. Urinary cadmium (U-Cd) and blood cadmium (B-Cd) levels were determined as indicators of Cd exposure. Urinary levels of ß(2)-microglobulin (ß(2)-MG), α(1)-microglobulin (α(1)-MG), N-acetyl-ß-D-glucosaminidase (NAG), cadmium-metallothionein (Cd-MT), and retinol binding protein (RBP) were determined as biomarkers of tubular dysfunction. U-Cd concentrations were increased linearly with time and dose, whereas B-Cd reached two peaks at 40 days and 100 days in the group exposed to 32mg Cd/kg. Hyper-metallothionein-urinary (HyperMTuria) and hyper-N-acetyl-ß-D-glucosaminidase-urinary (hyperNAGuria) emerged from 80 days onwards in the group exposed to 32mg Cd/kg feed, followed by hyper-ß2-microglobulin-urinary (hyperß2-MGuria) and hyper-retinol-binding-protein-urinary (hyperRBPuria) from 100 days onwards. The relationships between the Cd exposure dose and biomarkers of exposure (as well as the biomarkers of effect) were examined, and significant correlations were found between them (except for α(1)-MG). Dose-response relationships between Cd exposure dose and biomarkers of tubular dysfunction were studied. The critical concentration of Cd exposure dose was calculated by the benchmark dose (BMD) method. The BMD(10)/BMDL(10) was estimated to be 1.34/0.67, 1.21/0.88, 2.75/1.00, and 3.73/3.08mg Cd/kg feed based on urinary RBP, NAG, Cd-MT, and ß(2)-MG, respectively. The calculated tolerable weekly intake of Cd for humans was 1.4 µg/kg body weight based on a safety factor of 100. This value is lower than the currently available values set by several different countries. This indicates a need for further studies on the effects of Cd and a re-evaluation of the human health risk assessment for the metal.