Dummy template surface molecularly imprinted polymers based on silica gel for removing imidacloprid and acetamiprid in tea polyphenols.

Dummy template surface molecularly imprinted polymers based on silica gel were prepared through the surface molecular imprinting technique. Nonpoisonous nicotinamide, which is a structural analogue of imidacloprid and acetamidine, was chosen as the dummy template molecule. The obtained polymers were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The results showed that the polymers exhibited high adsorption capacity and selectivity for imidacloprid and acetamiprid. The maximum adsorption capacities of the polymers toward imidacloprid and acetamiprid were 42.05 and 22.99 mg/g, and the adsorption could reach binding equilibrium within 150 min. The polymers were successfully applied as column-filling materials to extract imidacloprid and acetamiprid from tea polyphenols with a relatively high removal rate (92.36 and 95.20%). The polymers also showed great stability and reusability during the application. The obtained polymers possessed good application prospects for removing imidacloprid and acetamiprid in tea polyphenol production processes.

Determinations of dinotefuran and metabolite levels before and after household coffee processing in coffee beans using solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry.

BACKGROUND: Coffee is one of the most popular beverages in the world. However, as daily consumables, coffee beans may contain pesticide residues that are capable of causing adverse health effects. Thus, we investigated residue dynamics in coffee beans using supervised field trials under Good Agricultural Practice conditions and determined the effects of household coffee processing on the coffee-bean pesticide residues dinotefuran and its metabolites 1-methyl-3-(tetrahydro-3-furylmethyl) urea (UF) and 1-methyl-3-(tetrahydro-3-furylmethyl) guanidine (DN). RESULTS: The recovery rate of dinotefuran and its metabolites UF and DN was in the range 73.5%-106.3%, with a relative SD < 10%. The limits of detection and limits of quantification for dinotefuran, UF and DN were all 0.003 and 0.01 mg kg-1 , respectively. Dissipation experiments were conducted over 2015 and 2016 and showed a mean half-life of 40.8 days. Coffee processing procedures were performed as described for traditional household coffee processing in Ethiopia. Dinotefuran contents were reduced by 44.4%-86.7% with washing of coffee beans and the roasting process reduced these contents by 62.2%-100%. DN residues were not detected in roasted coffee beans before day 21 or in brewed coffee before day 35 and UF residues were not detected in brewed coffee before day 35. Kruskal-Wallis analyses indicated large variations in the stability of pesticide residues between processing methods (P ≤ 0.05). Reductions of pesticide concentrations with washing were also significantly lower than those following roasting (P = 0.0001) and brewing processes (P = 0.002). Moreover, processing factors were less than one for all processing stages, indicating reductions of pesticides contents for all processing stages. CONCLUSION: The cumulative effects of the three processing methods are of paramount importance with respect to an evaluation of the risks associated with the ingestion of pesticide residues, particularly those in coffee beans. © 2018 Society of Chemical Industry.

Industrial prune processing and its effect on pesticide residue concentrations.

The aim of this study was to determine the insecticide residue processing factor (PF) from plums to prunes and the effect of the industrial processing of prunes residue concentrations. Our results show an increase of insecticide concentrations during plum dehydration that is explained by fruit water loss; however, the normalized insecticide residue concentration, based on plum dry weights to compensate dehydration, was reduced. The water washing and tenderizing of prunes produced insecticide residue reductions of 22.9 ±â€¯4.5% and 21.9 ±â€¯4.2%, respectively. PF were: 1.157, 1.872, 1.316, 0.192, 2.198, 0.775 and 0.156 for buprofezin, l-cyhalothrin, spirodiclofen, indoxacarb, acetamiprid, imidacloprid and emamectin benzoate, respectively, being directly related to water solubility, aqueous hydrolysis and degradation point and inversely related to molecular mass and melting point. In plums for the dehydrated agroindustry the final product is prunes, therefore, it is crucial to consider the PF to determine the specific preharvest interval for this important agroindustry.

Response surface methodology for the enantioseparation of dinotefuran and its chiral metabolite in bee products and environmental samples by supercritical fluid chromatography/tandem mass spectrometry.

Tracing the enantiomers of dinotefuran and its metabolite in bee products and relevant environmental matrices is vital because of the high toxicity of their racemates to bees. In this study, a statistical optimization strategy using three-dimensional response surface methodology for the enantioseparation of dinotefuran and its metabolite UF was developed by a novel supercritical fluid chromatography/tandem mass spectrometry (SFC-MS/MS) technique. After direct evaluation of the chromatographic variables - co-solvent content, mobile phase flow rate, automated backpressure regulator pressure (ABPR), and column temperature - involved in the separation mechanism and assessment of the interactions among these variables, the optimal SFC-MS/MS working conditions were selected as a CO2/2% formic acid-methanol mobile phase, 1.9mL/min flow rate, 2009.8psi ABPR, and 26.0°C column temperature using an amylose tris-(3,5-dimethylphenylcarbamate) chiral stationary phase under electrospray ionization positive mode. Baseline resolution, favorable retention, and high sensitivity of the two pairs of enantiomers were achieved in pollen, honey, water, and soil matrices within 4.5min. Additionally, the parameters affecting the dispersive solid-phase extraction procedure, such as the type and content of extractant or purification sorbents, were systematically screened to obtain better extraction yields of the enantiomers. Mean recoveries were between 78.3% and 100.2% with relative standard deviations lower than 8.0% in all matrices. The limits of quantification ranged from 1.0µg/kg to 12.5µg/kg for the dinotefuran and UF enantiomers. Furthermore, the developed method was effectively applied to authentic samples from a market, an irrigation canal, and a trial field, and the enantioselective dissipation of dinotefuran and UF in soil was demonstrated.

Consequences of the matrix effect on recovery of dinotefuran and its metabolites in green tea during tandem mass spectrometry analysis.

Determining the residues of dinotefuran and its metabolites (MNG, UF, and DN) is highly problematic because of their polar characteristics. Additionally, tea contains many compounds that can interfere with residue analysis. Thus, the aim of the present study was to refine the extraction method that assures good recoveries for dinotefuran and its metabolites and removes most of the matrix components in green tea using liquid chromatography-tandem mass spectrometry (LC/MS/MS). We attempted to increase the extraction efficiency of the QuEChERS method by selecting the appropriate solvents among ethyl acetate, acetone, isopropanol, 25% methanol in acetonitrile, and methanol. We found that methanol was the best extraction solvent for dinotefuran and its polar metabolites in dry green tea samples; however, due to a limitation of an appropriate partitioning salt, acetonitrile was used as the extraction solvent. Matrix enhancement and suppression effects were observed for all analytes, which made the recovery rates variable. DN recovery was <70% when compared with matrix-matched calibration, whereas it was within the acceptable range (70-120%) when compared with solvent calibration. The opposite was observed for MNG and dinotefuran due to a matrix suppression effect. UF recovery was consistent in both matrix-matched and solvent calibrations despite having little suppressive effect. The method was successfully applied and dinotefuran and its metabolite residues were found in field-incurred green tea samples. The current findings suggest that using methanol as an appropriate QuEChERS solvent for problematic polar pesticides and investigating a suitable partitioning salt would considerably strengthen the practical impact of such data.

Biotransformation of nitro-polycyclic aromatic compounds by vegetable and fruit cell extracts.

Extracts from various vegetables and fruits were investigated for their abilities to reduce nitro-polycyclic aromatic hydrocarbons (NPAHs). The extracts from grape and onion exhibited an interesting selectivity, yielding corresponding hydroxylamines or amines as major products under mild conditions of 30 °C and pH 7.0. Grape extracts reduced the 4-nitro-1,8-naphthalic anhydride with the highest conversion rate (>99%) and the highest ratio of hydroxylamine to amine (95:5). In contrast, the onion extracts reduced 4-nitro-1,8-naphthalic anhydride with a conversion rate of 94% and a ratio of hydroxylamine to amine of 8:92. The thiol-reducing agent, ß-mercaptoethanol, and metal cations, Ca(2+) and Mg(2+), greatly increased the reductive efficiency. This work provides an alternative strategy for biotransformation of nitro-polycyclic compounds.

Small-molecule inhibition of the interaction between the translation initiation factors eIF4E and eIF4G.

Assembly of the eIF4E/eIF4G complex has a central role in the regulation of gene expression at the level of translation initiation. This complex is regulated by the 4E-BPs, which compete with eIF4G for binding to eIF4E and which have tumor-suppressor activity. To pharmacologically mimic 4E-BP function we developed a high-throughput screening assay for identifying small-molecule inhibitors of the eIF4E/eIF4G interaction. The most potent compound identified, 4EGI-1, binds eIF4E, disrupts eIF4E/eIF4G association, and inhibits cap-dependent translation but not initiation factor-independent translation. While 4EGI-1 displaces eIF4G from eIF4E, it effectively enhances 4E-BP1 association both in vitro and in cells. 4EGI-1 inhibits cellular expression of oncogenic proteins encoded by weak mRNAs, exhibits activity against multiple cancer cell lines, and appears to have a preferential effect on transformed versus nontransformed cells. The identification of this compound provides a new tool for studying translational control and establishes a possible new strategy for cancer therapy.

A new iridoid glycoside from Linaria genestifolia.

A new iridoid glycoside named genestifolioside (1) was isolated from the ethanol extract of Linaria genestifolia. Its structure was defined by spectral analysis.

New aliphatic nitro-compounds from Indigofera carlesii.

An investigation of aliphatic nitro-compounds in Indigofera carlesii resulted in the identification of two blended novel compounds: 2-O-acryl-3,6-di-O-(3-nitropropanoyl)-alpha-d-glucopyranose and 6-O-acryl-2,3-di-O-(3-nitropropanoyl)-alpha-d-glucopyranose. The structures of the new compounds were elucidated on basis of spectral analysis.

[Identification of the structure of two new nitro group phenolic glycosides from Schisandra propinqua (Wall. ) Baill var. intermidia A. C. Smith].

AIM: To study the bioactive components from Schisandra propinqua (Wall.) Baill var. intermidia A. C. Smith. METHODS: Compounds were separated with a combination of multichromatography. Their chemical structures were determined on the basis of spectral analysis and chemical evidence. RESULTS: Seven compounds were isolated from the leaves of Helicia nilagirica. The structures were elucidated as 6'-O-alpha-L-arabinofuranosylthalictoside (1), 6'-O-beta-D-apiofuranosylthalictoside (2), thalictoside (3), icariside D2 (4), prinsepiol (5), (+)-1-hydroxypinoresinol (6) and (+)-medioresinol (7). CONCLUSION: Two compounds are new nitro phenolic glycosides.

Thalictricoside, a new phenolic compound from Thalictrum orientale.

From the underground parts of Thalictrum orientale Boiss., a new phenolic compound 1 was isolated in addition to one known cyanoglycoside, lithospermoside (2). For the structure elucidation of all compounds, 1D- and 2D-NMR techniques (DEPT, COSY, HMBC, HSQC) and MS (HR-MALDI) were used. The structure of the new compound was established as 2-(4'-hydroxyphenyl)-nitroethane-4'-O-[beta-xylopyranosyl-(1 --> 6)-beta-glucopyranoside] (1).