Rapid Quantitative Detection of Deltamethrin in Corydalis yanhusuo by SERS Coupled with Multi-Walled Carbon Nanotubes.

With the increase in demand, artificially planting Chinese medicinal materials (CHMs) has also increased, and the ensuing pesticide residue problems have attracted more and more attention. An optimized quick, easy, cheap, effective, rugged and safe (QuEChERS) method with multi-walled carbon nanotubes as dispersive solid-phase extraction sorbents coupled with surface-enhanced Raman spectroscopy (SERS) was first proposed for the detection of deltamethrin in complex matrix Corydalis yanhusuo. Our results demonstrate that using the optimized QuEChERS method could effectively extract the analyte and reduce background interference from Corydalis. Facile synthesized gold nanoparticles with a large diameter of 75 nm had a strong SERS enhancement for deltamethrin determination. The best prediction model was established with partial least squares regression of the SERS spectra ranges of 545~573 cm-1 and 987~1011 cm-1 with a coefficient of determination (R2) of 0.9306, a detection limit of 0.484 mg/L and a residual predictive deviation of 3.046. In summary, this article provides a new rapid and effective method for the detection of pesticide residues in CHMs.

Optimization of a Simplified and Effective Analytical Method of Pesticide Residues in Mealworms (Tenebrio molitor Larvae) Combined with GC-MS/MS and LC-MS/MS.

An effective analytical method was optimized for residues including chlorpyrifos-methyl, deltamethrin, fenoxanil, thiobencarb and fludioxonil in mealworms, the larval form of Tenebrio molitor. They are listed for pest control during wheat cultivation and can be found in wheat-bran feed for growing mealworms in South Korea. Analytes were extracted using acetonitrile and salt packet. Four clean-up methods ((1) MgSO4 + 25 mg PSA + 25 mg C18; (2) MgSO4 + 50 mg PSA + 50 mg C18; (3) EMR-lipidTM tube; and (4) 10 mL n-hexane) were investigated and the method (1) was selected due to its robustness. Low-temperature precipitation of fat and proteins improved the recoveries. Recoveries from the Method (1) were satisfying with 70-120% with <20% relative SD at a spiking level of 0.01 mg/kg. With the simultaneous sample preparation, fenoxanil, thiobencarb and fludioxonil were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) and chlorpyrifos-methyl and deltamethrin by gas chromatography tandem mass spectrometry (GC-MS/MS). Quantification limits for LC-MS/MS and GC-MS/MS were 0.5 and 2.5 µg/L, respectively. No pesticides of interest were detected in 30 real samples collected across the nation. However, the data can be provided for establishing maximum residue limits for the pesticides in mealworms in response to the positive list system.

Separation Processes to Provide Pure Enantiomers and Plant Ingredients.

Enantiomer separation and the isolation of natural products from plants pose challenging separation problems resulting from the similarity of molecules and the number of compounds present in synthesis or extract mixtures. Furthermore, limited theory is available to predict productivities for possible alternative separation techniques. The application and performance of chromatography- and crystallization-based processes are demonstrated for various case studies devoted to isolating valuable target compounds from complex initial mixtures. In all cases, the first emphasis is set to determine the process-specific phase equilibria to identify feasible process options. For all examples considered, yields and productivities are evaluated and compared for different scenarios. Guidelines to approach and solve similar separation tasks are given.

Effective preparation of magnetic molecularly imprinted polymer nanoparticle for the rapid and selective extraction of cyfluthrin from honeysuckle.

Cyfluthrin is a widely used pesticide. In this study, a sensitive and efficient magnetic molecularly imprinted polymer (MMIP) was prepared by surface molecular imprinting, which used functionalized Fe3O4 particles as magnetic cores. Cyfluthrin was extracted and enriched using magnetic molecularly polymer for analyzing pesticide residue of Chinese herbal medicines. The crystal type, microstructure, particle size, saturation magnetization, and characteristic functional groups of the synthesized MMIPs were analyzed by analysis equipment. The results of isothermal adsorption and kinetic adsorption indicated that MMIPs reached adsorption equilibrium at 30 min, with a maximum capacity of 4.9 mg g-1, which had good adsorption performance, while selective adsorption experiments showed that MMIPs had higher affinity for cyfluthrin. Under the optimized conditions, the limit of detection (LOD) and the limit of quantification (LOQ) were 32.987 ng ml-1 and 109.955 ng ml-1, respectively. And linear range (30-3000ng ml-1) of cyfluthrin with correlation coefficient R2=0.9979, and MMIPs were used in honeysuckle, the recoveries were 91.5%∼97.2%, and RSD was 5.35%∼8.32% (n = 3). It is indicated that the magnetic molecularly imprinted polymer can be used as an effective material for the specific separation of cyfluthrin from honeysuckle.

HPLC semi-preparative separation of diclazuril enantiomers and racemization in solution.

Diclazuril has been widely used in poultry feed for prevention and treatment of coccidiosis, and its chiral separation is rarely reported. Herein, semi-preparative separation method of diclazuril enantiomers has been developed through normal-phase high-performance liquid chromatography. Effects of chiral stationary phases, alcoholic modifiers, and column temperature on separation of diclazuril were discussed in detail. Both the single-urea-bound 4-chlorophenylcarbamoylated ß-cyclodextrin and amylose tris(3,5-dimethylphenylcarbamate)-coated chiral stationary phases showed strong ability in separation of diclazuril by using n-hexane-trifluoroacetic acid-ethanol. Then, semi-preparative separation of diclazuril was carried out through stacked injection, and the "enantiomeric excess" purities of two fractions were over 98%. Next, the electronic circular dichroism profiles of these two fractions in ethanol solution displayed the mirror image of each other in the range 360-200 nm. Moreover, effects of acidic/basic additive, time, and temperature on racemization of diclazuril enantiomers in ethanol solution have been studied in detail through normal-phase high-performance liquid chromatography. Racemization of diclazuril enantiomers was remarkably accelerated through adding triethylamine at high temperature. We envision that this systematic investigation of diclazuril at an enantiomeric level would provide valuable information in future studies involving enantioselective bioactive, metabolic, and toxicological activities.

Multiple response optimization of a QuEChERS extraction and HPLC analysis of diclazuril, nicarbazin and lasalocid in chicken liver.

A method for the simultaneous determination of three commonly used coccidiostats in chicken liver was developed, comprising a multi-residue QuEChERS (quick, easy, cheap, effective, rugged and safe) extraction step, and a liquid chromatography-ultra violet-fluorescence (HPLC-UV/FL) analysis. The QuEChERS extraction was optimized using an experimental design approach that includes a screening step to obtain the critical variables, an optimization step using multiple response surface analysis and the calculation of a desirability parameter. The optimized method was validated with fortified samples, reaching an average recovery of 91% and an overall precision of 5.5% (mean of three analytes at three levels). Limits of detection calculated on fortified samples were 20 µg kg-1 for lasalocid, 15 µg kg-1 for nicarbazin and 120 µg kg-1 for diclazuril. These values resulted at least one order of magnitude lower than the maximum allowed residue limit (MRL) of the studied coccidiostats for chicken liver.

Online estimation of optimal operating conditions for simulated moving bed chromatographic processes.

A new approach for determining optimal operating conditions for simulated moving bed chromatographic processes is presented. The method is based on recursive online estimation and requires only rough initial estimates. It is based on a simple foot point model of the moving concentration fronts and an online measurement of the corresponding retention times in the different zones of the plant. A mathematical representation of the adsorption isotherms is not required. The method is validated experimentally for the separation of bicalutamide enantiomers.

Solidification of floating organic droplet microextraction for determination of seven insecticides in fruit juice, vegetables and agricultural runoff using gas chromatography with flame ionization and mass spectrometry detection.

Liquid microextraction employing solidification of the floating organic droplet, with vortexing and heating to optimize extraction efficiency, was developed for the determination of seven insecticides in fruit juice, vegetables, and agricultural runoff water. The extracts were analyzed by gas chromatography with both flame ionization and mass spectrometry detection for the determination of chlorpyrifos, prothiofos, profenofos, ethion, λ-cyhalothrin, permethrin, and cypermethrin, respectively. Using 20 µL of 1-undecanol in 10 mL of aqueous solution containing 1% w/v sodium chloride provided preconcentration factor of 500. The enrichment factor of the analytes was in the range of 355 to 509 with extraction recovery >71%. The linearity ranges were 4-200 µg/kg for gas chromatography with flame ionization detection and 1-100 µg/kg for gas chromatography with mass spectrometry, with limits of detection ranging from 0.04 to 1.2 µg/kg, which are lower than the international maximum residue limits for vegetables and fruit juice. Intra-day and inter-day precisions are less than 5.4 and 7.0% relative standard deviation, respectively. The method was successfully applied to the determination of the seven insecticides in samples of vegetables, fruit juice and agricultural runoff, with recoveries ranging from 61.7 to 120.8%. The extraction method is simple, efficient and environmentally friendly.

Bioactive 2-(Methyldithio)Pyridine-3-Carbonitrile from Persian Shallot (Allium stipitatum Regel.) Exerts Broad-Spectrum Antimicrobial Activity.

Antibiotic resistance is a problem that continues to challenge the healthcare sector, especially in clinically significant pathogens like methicillin-resistant Staphylococcus aureus (MRSA). Herein is described the isolation and structure elucidation of a bioactive compound from Allium stipitatum with antimicrobial activity. Crude Allium stipitatum dichloromethane extract (ASDE) was subjected to systematic purification by chromatographic procedures to afford various bioactive fractions. A fraction that exhibited anti-MRSA activity (4 µg·mL-1) was further characterized to determine the structure. The structure of the compound was elucidated as 2-(methyldithio)pyridine-3-carbonitrile (2-Medpy-3-CN). The 2-Medpy-3-CN compound, which was screened for antimicrobial activity, exhibited minimum inhibitory concentrations (MICs) in the range of 0.5 to >64 µg·mL-1 for tested bacterial species and 0.25 to 2 µg·mL-1 for Candida spp. Further studies are important to confirm the drug target and mechanism of action.

Molecular snapshots of dynamic membrane-bound metabolons.

Numerous biosynthetic pathways have been shown to assemble at the surface of cellular membranes into efficient dynamic supramolecular assemblies termed metabolons. In response to environmental stimuli, metabolons assemble on-demand making them highly dynamic and fragile. This transient nature has previously hampered isolation and molecular characterization of dynamic metabolons. In contrast to conventional detergents, which tend to disrupt weak protein-protein interactions and remove lipids, the competence of a styrene maleic acid copolymer to carve out discrete lipid nanodisc from membranes offers immense potential for isolation of intact protein assemblies. Here, we present a method to extract the entire membrane-bound dhurrin pathway directly from microsomal fractions of the cereal Sorghum bicolor. This detergent-free nanodisc approach may be generally transposed for isolation of entire plant biosynthetic metabolons. This method provides a simple practical toolkit for the study of membrane protein complexes.

Centaurea microcarpa Coss. & Dur. (Asteraceae) extracts: New cyanogenic glucoside and other constituents.

The phytochemical investigation of both chloroform and ethyl acetate extracts of Centaurea microcarpa Coss. & Dur. led to the isolation of a new cyanogenic glucoside 6'-methacrylate prunasin (3) together with seven known compounds: hydroxy-11ß,13-dihydro onopordaldehyde (1), ß-sitosterol (2), daucosterol (4), nepetin (5), prunasin (6), astragalin (7) and 7-O-ß-D-glucopyranosyl centaureidin (8). Their structures were established by spectral analysis, mainly UV, IR, ESI-MS, 1D & 2D-NMR experiments (COSY, HSQC, HMBC and ROESY).

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.

Determination of four pyrethroid insecticides in water samples through membrane emulsification-assisted liquid-liquid microextraction based on solidification of floating organic droplets.

A novel membrane emulsification-assisted liquid-liquid microextraction method based on the solidification of floating organic drops was used to detect four pyrethroid pesticides (deltamethrin, etofenprox, fenpropathrin, and bifenthrin). In this method, [P44412]Br was used as a surfactant that could be removed from water via the addition of KPF6. The extraction solvent was separated after centrifugation and solidification on the water surface. The parameters affecting the recovery of the target compounds, including the surfactant amount, [P44412]Br-to-KPF6 molar ratio, addition of salt, extraction solvent volume, and temperature, were individually optimized and further analyzed through an orthogonal array design (OAD) experiment. The optimized conditions were based on the results of the OAD experiment and single-factor analysis. Using these experimental conditions, the recovery of the four pyrethroids ranged from 91.3% to 98.1% with relative standard deviation (RSD) values ranging from 1.7 to 2.2%. Good linearity was observed, with values from 0.9982 to 0.9997, and the linear range was between 1 and 500 µg/L (5-500 µg/L for fenpropathrin). The limit of detection (LOD) values based on a signal-to-noise ratio (S/N) of 3:1 were 0.37-0.75 µg/L. The enrichment factor ranged from 90 to 96. Therefore, this method is suitable for the determination of pyrethroid pesticides in environmental water samples.

Rapid, low temperature synthesis of molecularly imprinted covalent organic frameworks for the highly selective extraction of cyano pyrethroids from plant samples.

New imine-linked molecularly imprinted covalent organic frameworks (MICOFs) were successfully prepared, using fenvalerate as the dummy template. Schiff base reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-triformylphloroglucinol was rapidly achieved at room temperature, using Sc(OTf)3 as the catalyst. The surface groups and morphologies of MICOFs were assessed by Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller surface area analysis, and scanning electron microscopy. The MICOFs exhibited high selectivity toward four structurally similar cyano pyrethroids, including fenvalerate, flucythrinate, ß-cyfluthrin and λ-cyhalothrin. A method based on solid phase extraction using MICOFs coupled to high performance liquid chromatography was established for the determination of cyano pyrethroids in plant samples. Linearity in the range 0.1-200 ng g-1, with correlation coefficients of 0.9981-0.9993, was obtained for the four cyano pyrethroids. Detection limits and quantification limits were in the range 0.011-0.018 ng g-1 and 0.036-0.060 ng g-1, respectively. Recoveries at three spiked levels ranged from 94.3% to 102.7%. The developed method is thus a promising technique for the selective extraction of cyano pyrethroids from complex matrices.

Development and application of a novel fluorescent nanosensor based on FeSe quantum dots embedded silica molecularly imprinted polymer for the rapid optosensing of cyfluthrin.

A novel molecularly imprinted silica layer appended to FeSe quantum dots (MIP-FeSe-QDs) was fabricated and utilized as a recognition element to develop a selective and sensitive fluorescent nanosensor for cyfluthrin (CYF) determination. The MIP-FeSe-QDs were characterized by fluorescence spectrometry, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Excellent selectivity and high sensitivity of MIP-FeSe-QDs to CYF molecules were observed based on the fluorescence quenching of FeSe-QDs. Under optimal conditions, a good linear relationship was found between fluorescence quenching effect and increased CYF concentration within 0.010-0.20mg/L, with a correlation coefficient of 0.9911. The practicality of the developed sensor method for CYF detection in fish and sediment samples was further validated. Good recoveries ranging from 88.0% to 113.9% with<6.8% relative standard deviations were obtained. The detection limits of CYF in sediment and fish samples were 1.3 and 1.0µg/kg, respectively. This study established a novel, rapid fluorescent nanosensor detection method based on MIP-QDs for successfully analyzing CYF in fish and sediment samples.

Optimization and validation of RP-HPLC method for simultaneous estimation of palbociclib and letrozole.

A simple, rapid, and robust RP-HPLC method have been developed and validated to measure palbociclib (PB) and letrozole (LT) at single wavelength (254 nm). A isocratic elution of samples performed on Intersil C8 (4.6 mm × 250 mm particle size 5 µm) column with mobile phase consisting 0.02 M sodium dihydrogen phosphate buffer (pH 5.5): acetonitrile: methanol (80:10:10 v/v/v) delivered at flow rate 1.0 mL min-1. A good linear response was achieved over the range of 5-50 µg mL-1. The LODs for PB and LT were found to be 0.098 and 0.0821 µg mL-1, while the LOQs for PB and LT were 0.381-0.315 µg mL-1, respectively. The method was quantitatively evaluated in terms of system suitability test, linearity, precision, accuracy (recovery) and robustness as per standard guidelines. The method is simple, convenient and suitable for the analysis of PB and LT in bulk drug.

New sesquiterpenoid isonitriles from three species of phyllidid nudibranchs.

Chemical investigation of the two nudibranch species Phyllidiella pustulosa and Phyllidia ocellata collected in Queensland, Australia, provided new stereoisomers of 4-isocyano-9-amorphene (1) and of 10-isocyano-4-amorphene (2), respectively. A specimen of Phyllidia picta collected from Bali, Indonesia, contained the axane sesquiterpenoids pictaisonitrile-1 (3) and pictaisonitrile-2 (4). The planar structures were elucidated using 1D and 2D NMR spectroscopy, while relative configurations were established using NOESY correlations, coupling constant data, and comparison with literature data.

Characterization and application of a lanthanide-based metal-organic framework in the development and validation of a matrix solid-phase dispersion procedure for pesticide extraction on peppers (Capsicum annuum L.) with gas chromatography-mass spectrometry.

The metal-organic framework [(La0.9 Sm0.1 )2 (DPA)3 (H2 O)3 ]∞ was synthetized and characterized by X-ray diffractometry, differential thermogravimetric analysis, and infrared spectroscopy. The material was tested for the development and validation of a matrix solid-phase dispersion procedure for extraction of atrazine, bifenthrin, bromuconazole, clofentezine, fenbuconazole, flumetralin, procymidone, and pirimicarb, from peppers, with analysis using gas chromatography with mass spectrometry in the selected ion monitoring mode. The method developed was linear over the range tested (50.0-1000.0 µg/kg for procymidone and 200.0-1000.0 µg/kg for all other pesticides), with correlation coefficients ranging from 0.9930 to 0.9992. Experiments were carried out at 250.0, 500.0, and 1000.0 µg/kg fortification levels, and resulted in recoveries in the range of 52.7-135.0%, with coefficient of variation values between 5.2 and 5.4%, respectively, for [(La0.9 Sm0.1 )2 (DPA)3 (H2 O)3 ]∞ sorbent. Detection and quantification limits ranged from 16.0 to 67.0 µg/kg and from 50.0 to 200.0 µg/kg, respectively, for the different pesticides studied. The results were compared with literature data. The developed and validated method was applied to real samples. The analysis detected the presence of residues of pesticides procymidone, fenbuconazole, flumetralin, clofentezine, atrazine, and bifenthrin.

Pesticide residue removal in classic domestic processing of tomato and its effects on product quality.

This study was undertaken to evaluate the effectiveness of several household practices (washing with water or acidic, alkaline, and oxidizing solutions, and peeling) in minimizing pesticide residue contamination of tomatoes, as well as the impact on the quality of the treated fruit. Tests were performed using two systemic fungicides (azoxystrobin and difenoconazole) and one contact fungicide (chlorothalonil). Solid-liquid extraction with low temperature partition (SLE/LTP) and liquid-liquid extraction with low temperature partition (LLE/LTP) were used to prepare the samples for pesticides determination by gas chromatography. Washing the tomatoes with water removed approximately 44% of chlorothalonil, 26% of difenoconazole, and 17% of azoxystrobin. Sodium bicarbonate (5%) and acetic acid (5%) solutions were more efficient, removing between 32 and 83% of the residues, while peeling removed from 68 to 88% of the pesticides. The washing solutions altered some fruit quality parameters, including acidity and chroma, and also caused weight loss. Acetic acid (0.15 and 5%) and hypochlorite (1%) solutions had the greatest effect on these parameters.

Isolation of the antibiotic methyl (R,E)-3-(1-hydroxy-4-oxocyclopent-2-en-1-yl)-acrylate EA-2801 from Trichoderma atroviridae.

The endophytic Trichoderma atroviridae UB-LMA was isolated as a symbiont of Taxus baccata and analyzed for its antimicrobial activity. By applying an original approach consisting of solid-state cultivation coupled with solid-phase extraction, a new methyl (R,E)-3-(1-hydroxy-4-oxocyclopent-2-en-1-yl)-acrylate derivative named EA-2801 (1) was isolated together with the previously reported isonitrin A and dermadin methyl ester. The chemical structure of 1 was determined by NMR and MS. Compound 1 showed antimicrobial activity against a panel of Gram-positive and -negative bacteria.