Research method of rapid determination of chiral pesticide fenpropathrin enantiomers in fruit and vegetable puree by supercritical fluid chromatography.

A method is first established for the separation and determination of fenpropathrin enantiomer residues in apple puree, strawberry puree, and tomato puree considered a supplementary food for infants by supercritical fluid chromatography. After the sample was extracted with acetonitrile and cleaned up by a solid-phase extraction column, then it was separated by a CHIRALPAK AD-3 chiral column with gradient elution at a flow rate of 1.5 mL/min using methanol and supercritical carbon dioxide as the mobile phase, detected by ultraviolet detector at 230 nm wavelength and quantified with the external standard method. The limits of quantification of the two fenpropathrin enantiomers were both 0.2 mg/kg, the linear ranges were 1.0-20.0 mg/L with linear correlation coefficients greater than 0.9992, the recoveries in the spiked samples at 0.2, 0.4 and 2.0 mg/kg were from 80.6 to 105%, and the relative standard deviation reached 2.6-7.7%. This method has the advantages of convenient operation, good resolution, and environmental protection, which can satisfy the requirement of determination for fenpropathrin enantiomer residues in fruit and vegetable puree as supplementary food for infants.

Hydroxytyrosol and Oleuropein Inhibit Migration and Invasion via Induction of Autophagy in ER-Positive Breast Cancer Cell Lines (MCF7 and T47D).

Hydroxytyrosol (HT) and oleuropein (OL), the most abundant of the phenolic compounds in olives, have anticancer properties against breast cancer (BC). However, little attention has been paid to the mechanism of HT or OL in BC cells. The objective of this study was to identify the underlying molecular mechanisms of these compounds. ER-positive BC MCF7 and T47D cells were treated with HT and OL in combination with hepatocyte growth factor (HGF), rapamycin (Rapa, an agonist of autophagy) or 3-methyladenine (3-MA, an inhibitor of autophagy). Cell viability, metastasis capability and autophagy-related proteins were evaluated by wound healing assays, Transwell assays and Western blot. HT and OL reduced the cell viability of MCF-7 and T47D cells in a dose-dependent manner. Both cells were more sensitive to HT than OL. In addition, Rapa significantly inhibited HGF-induced migration and invasion, indicating that metastases of both BC cells could be inhibited by suppression of autophagy. Moreover, HT and OL significantly blocked HGF- or 3-MA-induced cell migration and invasion by reversing LC3II/LC3I and Beclin-1 downregulation and p62 upregulation. These findings revealed that HT and OL could suppress migration and invasion by activating autophagy in ER-positive BC cells, which might be a promising therapeutic strategy.

[Determination of four fatty acid ethyl esters in olive oil by solid phase extraction-gas chromatography].

The fatty acid ethyl ester (FAEE) content of olive oil is an important indicator of its quality. At present, the international standard method used to detect FAEEs in olive oil is silica gel (Si) column chromatography-gas chromatography (GC); however, this technique presents a number of disadvantages, including complex operation, long analysis times, and high reagent consumption. In this study, a method based on Si solid phase extraction (SPE)-GC was established to determine four FAEEs in olive oil, namely, ethyl palmitate, ethyl linoleate, ethyl oleate, and ethyl stearate. First, the effects of the carrier gas were investigated, and He gas was ultimately selected as the carrier gas. Next, several internal standards were screened, and ethyl heptadecenoate (cis-10) was determined as the optimal internal standard. The SPE conditions were also optimized, and the effects of different brands of Si SPE columns on the recoveries of analytes were compared. Finally, a pretreatment method in which 0.05 g of olive oil was extracted with n-hexane and purified through a Si SPE column (1 g/6 mL) was developed. A sample could be processed within approximately 2 h using a total reagent volume of about 23 mL. Validation of the optimized method revealed that the four FAEEs have good linearities within the range of 0.1-5.0 mg/L (coefficients of determination (R2)>0.999). The limits of detection (LODs) of the method were within 0.78-1.11 mg/kg, and its limits of quantification (LOQs) were in the range of 2.35-3.33 mg/kg. The recoveries ranged from 93.8% to 104.0% at all spiked levels tested (4, 8, and 20 mg/kg), and the relative standard deviations were 2.2%-7.6%. Fifteen olive oil samples were tested using the established method, and the total FAEEs of three extra-virgin olive oil samples were found to exceed 35 mg/kg. Compared with the international standard method, the proposed method has the advantages of simpler pretreatment process, shorter operation time, lower reagent consumption and detection cost, high precision, and good accuracy. The findings provide an effective theoretical and practical reference for improving olive oil detection standards.

New versatile zincic sorbent for tobacco specific nitrosamines and lead ion capture.

New carbon-doped ferric zinc oxide sorbents were fabricated to capture the environment carcinogen tobacco specific nitrosamines (TSNA) efficiently in solution, following new adsorption model of electrostatic attraction instead of traditional geometric constraints. The influence of ferric content on the structure-property of the sorbents was systemically studied with XRD, N2 adsorption-desorption and SEM methods combined with the adsorption of TSNA in different solutions. New sorbent captured 99% of 4-methylnitrosamino-1-3-pyridyl-1-butanone (NNK) in simulated surface water and 40% of TSNA in the tobacco extract solution, more than activated carbon or zeolites. Ferric ZnO sorbent took about 15 min to reach the adsorption equilibrium in the NNK or Pb(Ⅱ) solution, faster than NaZSM-5 zeolite. Moreover, the adsorbed NNK on ferric ZnO sorbent decomposed at mild conditions for the first time, providing a new way to control environment pollution.

Hydroxytyrosol and Oleuropein Inhibit Migration and Invasion of MDA-MB-231 Triple-Negative Breast Cancer Cell via Induction of Autophagy.

BACKGROUND: Breast Cancer (BC) is the leading cause of cancer-related deaths among women. As such, novel chemotherapeutic agents are urgently needed, especially for Triple-Negative Breast Cancer (TNBC). Hydroxytyrosol (HT) and Oleuropein (OL) are rich in olive oil, which is associated with a low occurrence of BC. However, the effects and mechanisms of action of HT and OL in BC cells are still unclear. This study aimed to explore the molecular mechanisms underlying the antitumor effect of HT and OL in TNBC. METHODS: TNBC MDA-MB-231 cells were treated with HT and OL in combination with Hepatocyte Growth Factor (HGF), rapamycin (Rapa, an inducer of autophagy) or 3-methyladenine (3-MA, an inhibitor of autophagy). Cell viability, migration, invasion, and autophagy signaling were analyzed by scratch assays, transwell migration assays, and Western blot analysis. RESULTS: Treatment with HT or OL reduced MDA-MB-231 cell viability in a dose-dependent manner. MDAMB- 231 cells were more sensitive to HT treatment than OL treatment. Rapa treatment could significantly block HGF-induced MDA-MB-231 cell migration and invasion, suggesting that inhibition of autophagy could promote migration and invasion. Moreover, HT or OL treatment significantly suppressed HGF or 3-MA induced cell migration and invasion by reversing LC3-II/LC3-I and Beclin-1 downregulation and reversing p62 upregulation. CONCLUSION: These data indicated that HT and OL may inhibit migration and invasion of TNBC cells by activating autophagy. These findings provide potential therapeutic strategies that target autophagy to limit the pathogenesis and progression of BC.

Determination of chloramphenicol in royal jelly by liquid chromatography/tandem mass spectrometry.

A liquid chromatographic/tandem mass spectrometric method was developed and validated for the determination of chloramphenicol (CAP) in royal jelly. Royal jelly samples were first denatured with lead acetate solution, and the CAP was extracted with solid-phase extraction before separation by liquid chromatography. A triple-quadrupole mass spectrometer operated in the negative electrospray ionization and selected-reaction monitoring mode was used for the detection of CAP. For method validation, royal jelly samples were fortified at CAP levels between 0.1 and 10.0 microg/kg; at these levels, recovery values (internal standard-corrected) ranged from 93.3 to 105.0%, and the within-laboratory reproducibility (relative standard deviation) was < or = 9.1%. The decision limit was 0.07 microg/kg, and the detection capability was 0.1 microg/kg.

Determination of 17 pyrethroid residues in troublesome matrices by gas chromatography/mass spectrometry with negative chemical ionization.

An analytical method with the technique of QuEChERS (quick, easy, cheap, effective, rugged and safe) and gas chromatography (GC)/mass spectrometry (MS) in negative chemical ionization (NCI) has been developed for the determination of 17 pyrethroid pesticide residues in troublesome matrices, including garlic, onion, spring onion and chili. Pyrethroid residues were extracted with acidified acetonitrile saturated by hexane. After a modified QuEChERS clean-up step, the extract was analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode. An isotope internal standard of trans-cypermethrin-D(6) was employed for quantitation. Chromatograms of pyrethroids obtained in all these matrices were relatively clean and without obvious interference. The limits of detection (LODs) ranged from 0.02 to 6 µg kg(-1) and recovery yields were from 54.0% to 129.8% at three spiked levels (20, 40 and 60 µg kg(-1) for chili, and 10, 20 and 30 µg kg(-1) for others) in four different matrices depending on the compounds determined. The relative standard deviations (RSDs) were all below 14%. Isomerization enhancement of pyrethroids in chili extract was observed and preliminarily explained, especially for acrinathrin and deltamethrin.