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Efficient enrichment of analytes and purification of matrices are crucial for the highly sensitive detection and monitoring of pesticides in traditional Chinese herbs. This work prepared magnetic ionic liquid-controlled covalent organic framework (IL-COF@Fe 3 O 4 ) as the sorbent via a simple in-situ precipitation polymerization and thiolene "click" strategy. The IL-COF@Fe 3 O 4 exhibited remarkable adsorption performance towards pyrethroids within 5 min. The adsorption of four pyrethroids on the surface of IL-COF@Fe 3 O 4 was according with Langmuir model and pseudo-second-order kinetic model. The adsorption energies were theoretically calculated, which were permethrin>cypermethrin>fenvalerate>bifenthrin. The modification of ILs improved extraction capacity mainly because of the interaction of imidazole and Cl or F and the pore size effect. This method was developed for the rapid extraction of four pyrethroids in Codonopsis pilosula and Angelica sinensis. The linear range was 0.05-200 μg L -1 . Matrix effects were ranging from -16.14% to 9.53%, indicating the strong matrix anti-interference ability of IL-COF@Fe 3 O 4 ., Competing Interests: Declaration of competing interest Authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier B.V. All rights reserved.)

In this study, a new magnetic biocompatible hydrogel was synthesized as an adsorbent for Deltamethrin pesticide removal. The optimal conditions and adsorption process of Deltamethrin by chitosan/polyacrylic acid/Fe 3 O 4 nanocomposite hydrogel was studied by Response Surface Methodology by Central Composite Design (RSM-CCD) and Artificial Neural Network (ANN). This adsorbents were synthesized, and then characterized and investigated using FT-IR, XRD, FE-SEM, EDX, Map, VSM, and TGA methods. The results of these analyses showed that the nanocomposite hydrogel was well synthesized and has the ability to adsorb the Deltamethrin pesticide. The results obtained through analysis using response surface methodology showed that the maximum amount of adsorption was 99.79 % at 26 °C, while pH, initial concentration, contact time, and adsorbent dose were 7, 22 ppm, 90 min, and 1.3 g/L respectively. Comparison between results obtained from CCD modeling and artificial neural network proved that both methods had high ability to predict the adsorption process but the CCD method had higher coefficient of determination and lower error. The equilibrium and kinetic study of the process showed that the Toth isotherm model, pseudo-second-order is all suitable for expressing the adsorption process. In addition, the adsorption mechanism followed double-exponential model that combines external and internal diffusions. Results of Thermodynamic study suggested that the Deltamethrin adsorption on CS/PAA/Fe 3 O 4 was a spontaneous and exothermic process. The results of the equilibrium process study revealed that the adsorption process was physical and desirable, therefore, the adsorption-desorption process was performed which showed that the composite was reusable up to 10 cycles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A novel temperature-responsive supramolecular solvent was prepared with cetyltributylphosphonium tetrafluoroborate and sodium citrate. It served as the extraction solvent of dispersive liquid-liquid microextraction for the extraction and enrichment of pyrethroids in tobacco samples. In this study, the preparation of the temperature-responsive supramolecular solvent and the extraction of the target analytes were integrated into one step, which simplified the experimental process. Due to the low melting point of the prepared supramolecular solvent, the traditional liquid-liquid separation can be converted to solid-liquid separation at low temperatures. This conversion facilitates precise collection of the supramolecular solvent and reduces the loss of target analytes. The composition, structure, physicochemical properties, and micromorphology of the supramolecular solvent were characterized. The formation and extraction mechanism of supramolecular solvent were explored, and the extraction conditions were optimized. The results indicated that good linearity of target analytes (R 2  > 0.9998) was obtained within the linear range. The limits of detection and quantification for the five pyrethroids were in the range of 0.25-0.50 μg L -1 and 0.85-1.65 μg L -1 , respectively. The present method can be used for the analysis of pyrethroid pesticide residues in tobacco samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this study, a spent mushroom substrate (SMS) from Lentinus edodes cultivation was used to prepare biochar (BC) and magnetic biochar (MBC) at high temperatures. The magnetic field strength of MBC was proved via VSM analysis. The results of the nitrogen adsorption‒desorption isotherms of BC and MBC showed that MBC exhibited stronger adsorption, and SEM was performed to compare the microstructures of BC and MBC. TEM was performed to compare the distributions of C, O, and Fe. The FT-IR and XRD results revealed changes in the structure and the formation of new substances after magnetization; that is, MBC was more conducive to the adsorption and recovery of pesticides. Moreover, a method for the detection of tetramethrin, beta-cypermethrin, and fenvalerate in water samples (tap water, lake water, and river water) was established, and this method combined the use of MBC as adsorbent and high-performance liquid chromatography. Moreover, great linearity of the method was obtained in the range of 0.5-2.5 μg/mL; the recoveries in real samples were in the range of 70.20-73.32 %, and the RSDs were in the range of 0.22-1.09 %. The method is simple and effective, is suitable for the detection of pyrethroids in water, and has certain application potential., Competing Interests: Declaration of competing interest No conflicts of interest exist regarding the submission of this manuscript, and the manuscript has been approved for publication by all authors. I declare on behalf of my co-authors that the work described here in represents original research that has not been published previously and is not under consideration for publication elsewhere, in whole or in part. All the listed authors have approved the enclosed manuscript., (Copyright © 2024. Published by Elsevier B.V.)

In this work, an imidazolium-based poly(ionic liquid) (poly(1-dodecyl-3-vinyl-imidazolium bromide) functionalized magnetic three-dimensional graphene oxide (Fe 3 O 4 @3D-GO@poly(ImC 12 + Br - )) was synthesized via a vacuum freezing-drying method and used as a magnetic solid phase extraction (MSPE) adsorbent for the efficient extraction of pyrethroid pesticides from tea samples. The prepared Fe 3 O 4 @3D-GO@poly(ImC 12 + Br - ) was confirmed by scanning electron microscopy (SEM), Fourier transform infrared spectrometry (FT-IR), vibrating sample magnetometer (VSM) and X-ray photoelectron spectrogram (XPS). Due to its large specific surface area and the ability to offer multiple intermolecular interactions, including π-π stacking, hydrophobic and hydrogen bond interactions, the prepared Fe 3 O 4 @3D-GO@poly(ImC 12 + Br - ) showed high extraction efficiency for pyrethroids. The experimental parameters were optimized by a combination of single-factor method and Box-Behnken design to improve the extraction efficiency. Under the optimum conditions, coupled with high performance liquid chromatography (HPLC), a sensitive analytical method was developed for the determination of pyrethroids, and the proposed method showed wide linear ranges (1.00-100 μg L -1 ) with correlation coefficients (R) ranging from 0.9980 to 0.9994, low limits of detection (0.100 μg L -1 ) and good repeatability with intra-day relative standard deviations (RSDs) in the range of 2.90-5.53 % and inter-day RSDs in the range of 1.83-7.76 %. Moreover, the developed method was successfully applied to the determination of pyrethroids in tea samples and satisfactory recoveries ranging from 82.37 % to 114.34 % were obtained. The results showed that the developed Fe 3 O 4 @3D-GO@poly(ImC 12 + Br - ) was an ideal, effective and selective material for the extraction and enrichment of pyrethroids from tea samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A novel bio-supramolecular solvent (bio-SUPRAS) based on rhamnolipids (RLs) was designed for efficient extraction of pyrethroid insecticides in water and food matrices. Benefiting from RLs as amphiphiles equipped with the attractive properties of bio-degradable, low toxicity and high stability, bio-SUPRAS was spontaneously generated through salt induced coagulation. The bio-SUPRAS was characterized by cryo-scanning electron microscope and main factors influencing the extraction performance were investigated in detail. Under the optimized conditions, the method was found to have desirable limits of detection (5∼10 μg l -1 ), good precision (RSDs<16.9 %) and satisfactory recovery (75.2 %∼94.3 %). More importantly, the extraction mechanism was studied by density functional theory systematically. Following greenness assessment, the technique was successfully used for enrichment of pyrethroid pesticides in real samples before HPLC-UV analysis. Thus, the method showed the outstanding merits of eco-efficient, green, time-saving, and had favorable application prospect to remove trace analytes from intricate sample matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study explores the reduction of carbamates (CAs) and pyrethroids (PYs) - commonly used pesticides - in lettuce using various immersion solutions and ultrasonic processing. It also examines the role of machine learning and molecular docking in understanding the mechanisms of pesticide reduction. The results revealed that the highest reduction of both CAs and PYs exceeded 80 % on lettuce leaves. In most samples, the reduction increased with the power of ultrasonic processing and processing time. The results of machine learning models (XGBoost and SHAP) showed that during the immersion cleaning of CAs and PYs, as well as during both immersion cleaning and ultrasonic processing of CAs + PYs, the reduction was most influenced by the initial pesticide levels and immersion time. Gas Chromatography-Mass Spectrometry (GC-MS) analysis of lettuce's wax layer identified 24 compounds, including fatty alcohols, fatty acids, fatty acid esters, and triterpenoids. Despite the absence of active sites, the lipophilic nature of long-chain aliphatic compounds aids in pesticide binding, while triterpenoids form strong hydrogen bonds with pesticides, indicating a robust adsorption on the lettuce surface. This study aims to offer insights into the efficient removal of chemical pesticide residues from fruits and vegetables, addressing critical concerns for food safety and human health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Background: Pesticides are used in agricultural production for prevent and control crop diseases and pests, but it is easy to cause excessive pesticides residues in agricultural products, polluting the environment and endangering human health. Due to their unmatched and sustainable capabilities, nanoextraction procedures are becoming every day more important in Analytical Chemistry. In particular, nanoconfined liquid phase extraction has shown extraction capabilities toward polar, medium polar, and/or nonpolar substances, which can be easily modulated depending on the nanoconfined solvent used. Furthermore, this "green" technique showed excellent characteristics in terms of recoveries, extraction time (≤1 min), reliability, and versatility. (97) RESULTS: In this work, the advantages of this technique have been coupled with those of filtration membrane extraction, making use of carbon nanofibers (CnFs) growth on carbon microspheres (CμS). This substrate has been deposited on a filter, which combined with gas chromatographic mass spectrometry (GC-MS) analysis successfully employed for the nanoextraction of 30 pesticides (18 organochlorine and 12 pyrethroids) in tea samples. Under the optimized extraction conditions, the linear range with standard solutions was from 1 to 1000 ng mL -1  (R 2  ≥ 0.99), the limit of detections in tea samples were in the range 0.56-17.98 μg kg -1 . The accuracy of the developed method was evaluated by measuring the extraction recovery of the spiked tea samples, and recoveries between 74.41 % and 115.46 %. (119) SIGNIFICANCE: Considering the versatility of nanoconfined liquid phase extraction and the functionality of the filtration membrane extraction procedure, this new extraction method can be considered a powerful candidate for automatized high-throughput analyses of real samples. (34)., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A simple technique was developed for the modification of cotton materials that is inexpensive, environmentally friendly, and very effective. Waste Cotton fabrics (WCFs) are loaded with propolis extract (PE) for Cu 2+ removal. Then, Cu 2+ underwent a pyrolysis process with modified cuttlebone (CB) at 900 °C for 5 h. The surface of the prepared materials was characterized using X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray (SEM-EDX), Fourier transform infrared (FTIR), BET, particle sizes, thermogravimetric analysis (TGA) and zeta potential analysis. The Cu 2+ metal ions from an aqueous solution were removed using WCFs/PE, and DLM was subsequently removed using pyro WCFs/PE/Cu/CB. The as-prepared NPs exhibited the face-centered cubic structure of WCFs/PE/Cu/CB with crystallite sizes ranging from 386.70 to 653.10 nm. FTIR spectra revealed that CB was present on the surface of the resulting WCFs/PE/Cu. SEM revealed the dispersion of a uniformly flower-like morphology over a large area. Sorption studies were performed based on parameters that included pH, dose, contact time, and initial concentration. The adsorption isotherm and the kinetic studies of the DLM adsorption process were applied at a pH of 5.0 and a temperature of 25 °C using several isotherms and kinetic models. The results revealed q max (20.51 mg/g) with R 2  = 0.97, the Langmuir isotherm that best matches the experimental data. Hence, the Langmuir isotherm suggests that it is the model that best describes sorption on homogenous surfaces or surface-supporting sites with various affinities. The correlation coefficient R 2 , χ 2 , adjusted correlation coefficient, and error functions like root mean square (RMSE), normalized root mean square error (NRMES), and mean absolute error (MAE) were used to evaluate the best-fit models to the experimental adsorption data. Moreover, cost estimation for the prepared adsorbent WCFs/PE/Cu showed that it costs approximately 3 USD/g, which is a cheap adsorbent compared to other similar adsorbents reported in the literature. The examined WCFs/PE have significant applicability potential for Cu 2+ -laden wastewater treatment due to their superior Cu 2+ metal ions adsorption capability and reusability. The cytotoxicity and safety study showed that at higher concentrations, it resulted in much less cell viability. Additionally, the removal efficiency of Cu 2+ metal ions from synthetic, realistic industrial wastewater using WCFs/PE reached up to 96.29 %, demonstrating good adsorption capability. Thus, there is a huge possibility of accomplishing this and performing well. This study paves the way for the reuse and valorization of selected adsorbents following circular economy principles. Two green metrics were applied, the Analytical Eco-scale and the Analytical GREEnness Calculator (AGREE)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Nowadays, the development of sustainable molecularly imprinted polymers (MIPs) with high selectivity is still challenging due to the limitations of bio-based functional monomers. In this study, the highly selective and porous MIPs (LC-TMIPs) were designed and prepared on short amylose (SAM) as bio-based functional monomers, λ-cyhalothrin (LC) as a template molecule, and tetrafluoroterephthalonitrile as a rigid crosslinking agent. Static, dynamic, and selective adsorption experiments were conducted to investigate the adsorption performance. The results indicated that, compared to MIPs prepared using epichlorohydrin as flexible crosslinking agents, LC-TMIPs exhibited higher imprinting factor (3.93), selectivity (5.78), and adsorption capacity (35.79 mg g -1 ), as well as faster adsorption/desorption kinetics. The LC-TMIPs were used as sorbents for the selective determination of LC in both apple and cucumber samples by high-performance liquid chromatography. Under the optimal extraction conditions, the recoveries of the method reached 92.1-106.1 %, with a linear range of 1.5-30 ng g -1 and a detection limit of 0.5 ng g -1 . The proposed preparation method of LC-TMIPs is expected to open a new way to prepare highly selective and sustainable MIPs for hydrophobic compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO 2 @Fe 3 O 4 as an adsorbent. COF-SiO 2 @Fe 3 O 4 was prepared by a straightforward solvothermal method, using Fe 3 O 4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO 2 @Fe 3 O 4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 μg·kg -1 (1.00-100 μg·kg -1 for bifenthrin and 2.5-100 μg·kg -1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 μg·kg -1 , and the limits of quantification (LOQs) were 0.9-4.5 μg·kg -1 . The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO 2 @Fe 3 O 4 , NH 2 -SiO 2 @Fe 3 O 4 and Fe 3 O 4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO 2 @Fe 3 O 4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.

Synthetic pyrethroids are frequently detected as trace contaminants in sediment and natural waters. Because of the importance of measuring both total and freely available concentrations for ecotoxicity evaluations, solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry using negative chemical ionization (NCI-GC-MS) was investigated as an analytical technique. Automated SPME-NCI-GC-MS quantification of freely dissolved (and thus potentially bioavailable) pyrethroids in aqueous samples containing dissolved organic matter (DOM) was successfully applied. The introduction of stable isotope-labeled pyrethroid calibration standards into the water sample allows for the simultaneous determination of total concentrations. Because pyrethroids adsorb rapidly to container walls (especially in calibration standard solutions without DOM) it was necessary to develop a technique to minimize the resulting time-dependent losses from calibration standard solutions in autosampler vials as they await analysis. A staggered preparation of these analytical calibration standards immediately prior to analysis was shown to ameliorate this problem. The developed method provides accurate and reproducible results for aqueous samples containing a range of dissolved organic matter concentrations (e.g., sediment pore water or sediment/water mixtures) and yields practical benefits in comparison to conventional analysis methods, such as reduced sample volume requirements, reduced solvent consumption, and fewer sample manipulations, and makes simultaneous measurements of freely dissolved/bioavailable pyrethroids and total pyrethroids possible.

Background: Variability of pesticide residues in food item plays a key role for the evaluation of consumer food safety. However, variability factors (VFs) derived from the large size fruit crops are still scarce. Therefore, the present work was aimed to quantify pesticide residues and to estimate VFs in large size fruit crops of mango and guava., Results: A total of 140 mango and 130 guava samples from different marketplaces in Bangladesh were collected to estimate the variability of pesticide residues (acephate, diazinon, malathion, fenitrothion, chlorpyrifos, quinalphos, dimethoate and cypermethrin) by in-house validated methods based on modified QuEChERS extraction and gas chromatography coupled with electron capture detector (ECD) and flame thermionic detector (FTD). The method was validated at three fortification levels (0.01, 0.10 and 0.30 mg kg -1 ) and satisfactory recoveries (80-111%) with relative standard deviation (RSD r ) ≤ 13% were achieved. A wide variation of residues was found in the analyzed samples. In the case of mango, the ranges of residues were 0.011-0.314, 0.015-0.04, and 0.05-0.291 mg kg -1 , respectively, for cypermethrin, chlorpyrifos, and dimethoate, while in the case of guava, the ranges were 0.04-0.113, and 0.03-0.290 mg kg -1 , respectively, for cypermethrin and acephate. The average VF for mango was 4.06 and it was 5.70 for guava., Conclusion: VFs originating from the marketed samples of mango and guava are reported in this study for the first time. The estimated VFs were higher than the default value of 3, therefore, the default VFs should be reconsidered when more data are obtained regarding large size crops. © 2021 Society of Chemical Industry., (© 2021 Society of Chemical Industry.)

The changes in residual amounts of an insecticide (etofenprox) in processed rice cakes and cookies were investigated in this study. Test samples were sprayed with etofenprox during rice cultivation, and brown rice samples were dipped in a pesticide solution to investigate the effects of washing and processing. A multiresidue method for multiclass pesticides was employed for etofenprox analysis using a high-performance liquid chromatography-ultraviolet detector setup. Etofenprox was not detected in polished rice that was processed into rice cakes and cookies. The etofenprox residue levels were 2.13 mg/kg in each processing stage of brown rice products that were dipped in 400 mg/kg etofenprox solutions. The residual amounts of etofenprox in washed/polished rice and rice flour obtained by grinding were 1.25 and 0.77 mg/kg, respectively. The residual levels were 0.38 mg/kg in rice cakes prepared by cooking rice flour in a steamer for 20 min (a decrease of 82.1% compared to that in polished rice), 0.47 mg/kg in rice cookies baked in an oven for 20 min (a decrease of 78.0%), and 0.21 mg/kg in fried rice cookies (a decrease of 90.2%). Overall, the residual levels of etofenprox decreased in a range of 40-100% during the processing of rice cakes and cookies., Competing Interests: The authors have declared that no competing interests exist.

Magnetic hyperbranched polyamideamine was carboxylated using succinic anhydride and modified further with 1-octyl-3-methylimidazole hexafluorophosphate successively. The morphology and chemical composition of the prepared material was characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller measurement, X-ray photoelectron spectroscopy, etc. 1-Octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine was used as sorbent in the magnetic solid-phase extraction for the separation and enrichment of five pyrethroid insecticides from tea infusion. The magnetic solid-phase extraction method proposed in this article has low method detection limits (0.53-0.71 ng/mL), acceptable coefficient of determination (0.9992-0.9998), wide linear ranges (2.5-500.0 ng/mL), and good repeatability (intraday: 1.2-6.3%; interday: 1.6-5.4%). In the detection of five pyrethroid insecticides in tea infusion, relative recoveries were in the range from 87.7 to 114.7% with satisfactory relative standard deviations (0.2-7.4%). With the aid of quantum chemistry calculations, the interaction energy between the sorbent and five pyrethroid insecticides was calculated, which proved the necessity of the modification of 1-octyl-3-methylimidazole hexafluorophosphate., (© 2021 Wiley-VCH GmbH.)

In this study, the cypermethrin binding characteristics of lactic acid bacteria were investigated for the first time. Two strains, Lactobacillus plantarum RS60 and Pediococcus acidilactici D15, possessed the highest cypermethrin removal capacity and good tolerance to simulated digestive juices. They were employed for further studies on cypermethrin binding characteristics. 55.06% and 56.46% of cypermethrin were removed within 0.25 h by strains RS60 and D15, respectively. The effect of pH on binding capacity was negligible. Heat treatment enhanced cypermethrin binding rate. Moreover, inactive cells were capable of removing cypermethrin from fruit and vegetable juices, with over 60% cypermethrin reduction within 2 h. No adverse effect was found on the quality of juice during the biosorption process. Besides, these two strains also could bind other several pyrethroids and 3-phenoxybenzoic acid. These findings indicated that L. plantarum RS60 and P. acidilactici D15 may be useful to reduce cypermethrin in contaminated foods., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Pyrethroids insecticides may constitute a major hazard to honeybees, leading to colony collapse disorder. However, the determination of pyrethroids in honey has remained a challenging undertaking for analysts to date due to the high complexity of this matrix as well as the MRLs. This paper presents a fully automated method to overcome matrix influences using matrix-compatible overcoated SPME fiber for quantitative analysis of pyrethroids in diluted honey by GC-MS. The developed method was optimized using a multivariate approach providing LOQ values much lower than the stablished MRL (0.10-10 ng/g), while granting satisfactory linearity (R 2  > 0.998) in a wide linear range of 0.1-2000 ng/g, repeatability with RSDs < 10%, reproducibility RSDs < 20%, and accuracy ranging from 75 to 118% and from 82 to 120 % for inter-day and intra-day assays, respectively by using five replicates. The method herein proposed overcomes challenges presented by complex matrices while minimizing sample handling and the overall complexity of the procedure., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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 ( R 2 ) 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.

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) MgSO 4 + 25 mg PSA + 25 mg C18; (2) MgSO 4 + 50 mg PSA + 50 mg C18; (3) EMR-lipid TM 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.

A simple, green and efficient method for extraction, purification and enrichment of pesticide residues of triazoles and pyrethroids in Longan fruit was developed by ultrasonic-assisted aqueous two-phase extraction (UAATPE) coupled to vortex-assisted dispersive liquid-liquid microextraction (VADLLME). Using an aqueous two-phase system (ATPS) of ethanol/K 2 HPO 4 as extraction solvent, the composition of the ATPS, extraction temperature and time were investigated, respectively. Then VADLLME process also was optimized by investigating type and volume of extracting and dispersive solvents, vortex-assisted time and salt addition. The optimum conditions were as follows: the ATPS composition of ethanol concentration 30.0% (w/w) and K 2 HPO 4 concentration 25% (w/w), extraction temperature 70 °C and extraction time 15 min for UAATPE; 1-dodecanol 200 μL as extraction solvent, ethanol 1.25 mL as dispersive solvent, vortex-assisted time 1.5 min and addition of NaCl 4% (w/v) for VADLLME. Ethanol as extraction solvent and dispersive solvent could directly connect UAATPE with VADLLME without extra steps. By means of HPLC-DAD detection, nine pesticides had good linearity ranged from 0.0200 to 13.59 μg/mL (R 2  ≥ 0.9957). LODs and LOQs were in the range of 0.005576-0.01740 μg/mL and 0.01859-0.05010 μg/mL, respectively. UAATPE-VADLLME coupled to HPLC was successfully applied to simultaneous determination of multiple pesticides in Longan fruit, and mean recoveries and RSDs were between 76.95% and 98.63%, 1.2% and 9.8%, respectively. Furthermore, myclobutanil, fenpropathrin and deltamethrin were detected in pericarp and pulp of Longan samples from different districts, respectively., Competing Interests: Declaration of Competing Interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

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 Fe 3 O 4 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 R 2 =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.

A simple, sensitive and environmentally-friendly method for determining organophosphorus and pyrethroid pesticides in vegetables was developed to better evaluate the risk of consuming them. The pesticides in vegetables were extracted, purified and concentrated by using the QuEChERS (quick, easy, cheap, effective, rugged and safe method) combined DLLME-SFO (dispersive liquid-liquid microextraction based on solidification of floating organic droplet) techniques. The key parameters were optimized through orthogonal array experimental design and statistical analysis. The linearity of the calibration curves was satisfied in matrix-matched standard solution with R 2  ≥ 0.99. The limits of detection and limits of quantification were 0.3-1.5 and 0.9-4.7 μg/kg, respectively. The average recoveries of pesticides were 61.6-119.4% with relative standard deviations <16.1%. Furthermore, the method was applied successfully to analyse the pesticides in 15 pairs of organic and conventional vegetables. These results reflect the efficiency, reliability and robustness of the developed method., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Pyrethrum extract is a natural insecticide that has been used worldwide for centuries, with pyrethrins being considered active ingredients. Their purification is difficult due to their chemical structural similarity and instability to light. In the present study, a coordination complex high-speed counter-current chromatography was used to separate pyrethrins from pyrethrum extract. The two-phase solvent system composed of petroleum ether-ethyl acetate-methanol-water (10:2:10:2, v/v/v/v) with 0.30 mol/L silver nitrate was selected for separation. As a result, five pyrethrins including cinerin II (31.2 mg), pyrethrin II (43.9 mg), jasmalin II (39.1 mg), pyrethrin I (32.4 mg), and jasmalin I (16.0 mg) were obtained from 400 mg crude extract in 6 h by one-step HSCCC separation, with purities over 95%. The isolated compounds were identified by MS, 1 H-NMR and 13 C-NMR spectroscopy. The results demonstrated that the addition of silver nitrate in the two-phase solvent system of HSCCC significantly increased the HSCCC separation factor of pyrethrins. HSCCC is a rapid method for purification of pyrenthrins from pyrethrum extract. The established method may also be applied to separate analogous compounds from natural products in which the chemical structure differs in the position or numbers of alkenes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019. Published by Elsevier B.V.)

A simple, sensitive and effective magnetic solid-phase extraction (MSPE) technique was developed for the extraction of pyrethroid pesticides from environmental water samples, followed by gas chromatography tandem triple quadrupole mass spectrometry determination. An adsorbent of magnetic zeolitic imidazolate framework-8@deep eutectic solvent (M-ZIF-8@DES) was prepared using deep eutectic solvent coated on the surface of M-ZIF-8. The features of M-ZIF-8@DES were confirmed by material characterizations, and the results indicated that M-ZIF-8@DES has a good magnetism (61.3 emu g -1 ), a decent surface area (96.83 m 2 g -1 ) and pore volume (0.292 mL g -1 ). Single factor experiments were carried out to investigate the effect of different conditions on the performance of MSPE. Under the optimal conditions, the developed method performs good linearity (R 2 ≥ 0.9916) in the concentration range of 1-500 μg L -1 . The limits of detection were in the range of 0.05-0.21 μg L -1 (signal/noise = 3/1). The intraday relative standard deviation (RSD) and interday RSD were less than 9.40%. Finally, the proposed technique was applied for the determination of pyrethroid pesticides in environmental water samples. This work shows the potential of DES-modified metal-organic frameworks for different sample pretreatment techniques.

The presence of the pyrethroids residues in different samples and the impact on human health is an increasing concern due to their widespread use. So, a method to determine eighteen pyrethroids in fish samples using a modified QuEChERS was developed. The clean-up procedure was performed by freezing samples overnight followed by dispersive solid phase extraction. The combination of C 18 , PSA and Z-Sep+ was optimized using a mixture design approach and samples were analysed using gas chromatography mass spectrometry. The method was validated using trahira samples and a scope extension was performed for tilapia and tainha. Recoveries were within 63-129%, relative standard deviation was ≤21.5% and the quantification limits were 5 µg kg -1 or 10 µg kg -1 . The applicability of the method was assessed by analysis of fourteen real samples, in which residues were detected in four samples. Such detections demonstrate the importance of this sensitive method., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

There is a growing concern to pesticide exposure in humans, being the organophosphate (OP), carbamate and pyrethroid the most commonly used insecticides. Therefore, a fast, simple and automated screening method based on ultra-high performance liquid chromatography coupled to Orbitrap high resolution mass spectrometry (UHPLC-Orbitrap-MS) has been developed to determine six OPs metabolites (3,5,6-trichloro-2-pyridinol "TCPy", 2-isopropyl-6-methyl-4-pyrimidinol "IMPY", 4-nitrophenol "PNP", 4-nitrophenol-d4 "PNP-d4″, 3-chloro-7-hydroxy-4-methylcoumarin "CMHC" and 2-diethylamino-6-methylpyrimidin-4ol "DEAMPY") and three pyrethroid metabolites (3-phenoxybenzoic acid "3-PBA", 4-fluoro-3-phenoxybenzoic acid "4-F-3-PBA" and 3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid "cis/trans-DCCA") in human urine samples. Off-line solid phase extraction (SPE), on-line SPE and turbulent flow chromatography (TurboFlow ™ ) extraction methodologies were compared, obtaining better results when TurboFlow ™ was applied, achieving a total analysis time of 13.83 min. Several validation parameters were tested, obtaining suitable results for all studied compounds. Recoveries ranged from 70 to 116%, meanwhile repeatability and reproducibility were lower than or equal to 7% and 13%, respectively. The limits of quantification (LOQs) were set in the range from 1 μg/L to 5 μg/L (except for DCCA at 10 μg/L). Finally, thirty seven urine samples from women and men living near the agricultural areas of Almeria (Spain) were analyzed to know and control the contamination on the human health. PNP, DEAMPY and IMPY were detected in six urine samples at trace levels except IMPY, which was detected at 3.44 μg/L in one of the samples. Additionally, a post-targeted and untargeted analysis were carried out in the samples, identifying eleven insecticides such as bensulide or cinerin II, one insecticide metabolite, fipronil sulfone, one drug metabolite, carboxyibuprofen and two nicotine metabolites, cotinine and 2-(1-pyrrolidinyl)isonicotinic acid, in several samples., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This manuscript presents an effective and robust method for simultaneous stereoselective determination of two pyrethroid insecticides, tetramethrin and α-cypermethrin in different food products by high-performance liquid chromatography. Enantioseparation was carried out using reversed-phase chromatography, and the influences of four polysaccharide-based chiral columns, mobile phase composition, and column temperature on retention were fully investigated. Satisfactory separation was obtained on Chiralpak IG column using acetonitrile-water (75:25, v/v) under isocratic conditions. To extract and purify the target analytes from food matrices, matrix solid-phase dispersion was employed with C 18 as dispersant and primary secondary amine as well as graphitized carbon black as cleanup sorbents. Response surface method based on Box-Behnken design was implemented to assist optimization of the extraction variables. Then, method validation was done in real samples including specificity, linearity, sensitivity, trueness, precision, as well as stability, and its analytical performance fulfills the criteria recommended by the European Union SANTE/11945/2015, demonstrating its applicability in studying the stereochemistry of chiral tetramethrin and α-cypermethrin in food products.

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., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This work describes a hybrid electrochemical sensor for highly sensitive detection of pesticide cypermethrin (CYP). Firstly, Ag and N co-doped zinc oxide (Ag-N@ZnO) was produced by sol-gel method, and then Ag-N@ZnO was ultrasonically supported on activated carbon prepared from coconut husk (Ag-N@ZnO/CHAC). Finally, a layer of molecularly imprinted polymer (MIP) was in situ fabricated on glassy carbon electrode by electro-polymerization, with dopamine and resorcinol as dual functional monomers (DM), CYP acting as template (DM-MIP-Ag-N@ZnO/CHAC). Morphological features, composition information and electrochemical properties of DM-MIP-Ag-N@ZnO/CHAC were investigated in detail. It is worth to mention that for the first time response surface method was used to investigate the effect of double monomers and to optimize the ratio between template and monomers. Compared with typical one-monomer involving MIP, the MIP prepared with dual functional monomers (DMMIP) of monomers showed higher response and better selectivity. Under the optimal conditions, a calibration curve of current shift versus concentration of CYP was obtained in the range of 2 × 10 -13 ~8 × 10 -9 M, and the developed sensor gave a remarkably low detection limit (LOD) of 6.7 × 10 -14 M (S/N = 3). Determination of CYP in real samples was conducted quickly and accurately with our sensor. The DMMIP-Ag-N@ZnO/CHAC electrochemical sensor proposed in this paper has great potential in food safety, drug residue determination and environmental monitoring., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A commercial pyrethrum extract was used as a source of chrysanthemol for the synthesis of the citrophilus mealybug ( Pseudococcus calceolariae) sex pheromone. The chrysanthemic acid esters (pyrethrins I) were isolated and subsequently reduced to obtain chrysanthemol, which was used for ester pheromone synthesis. Field tests showed that the pheromone synthesized using plant-derived chrysanthemol was as attractive to male P. calceolariae as the pheromone obtained using a commercial isomeric chrysanthemol mixture.

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 ± 4.5% and 21.9 ± 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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A novel dispersive magnetic solid phase microextraction method based on ionic liquid-coated and cyclodextrin-functionalized magnetic core dendrimer nanocomposites has been developed for the determination of pyrethroids in juice samples. The different generation magnetic core dendrimer nanocomposites were successfully synthesized and the nanocomposites possess both the selective retention of guest dendrimer and cyclodextrin molecules and high adsorption capacities of ionic liquids. The extraction efficiencies of different generation magnetic core dendrimer nanocomposites were compared, and the type of nanocomposite with the highest recovery was obtained. Under the optimized experimental conditions, the method showed good linearity in the range of 3.5-500 μg L -1 . The LODs and LOQs were in the ranges of 0.36-1.3 μg L -1 and 1.2-4.3 μg L -1 , respectively. The method also showed acceptable accuracies ranging from 98.2% to 99.4%. The proposed method was demonstrated to broaden the potential applications of dendrimer for the detection of pyrethroid residues in various juice samples., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A sensitive and reproducible screening analytical method is described for the determination of six pyrethroids (phenothrin, permethrin, cyfluthrin, cypermethrin, deltamethrin, fenvalerate) in egg and meat samples by gas chromatography and electron capture detection (GC-ECD). A fast cleanup procedure, based on solid-phase extraction has been used, ensuring reduced solvent consumption and time and allowing the simultaneous preparation of multiple sample extracts. Under the optimal chromatographic conditions, an efficient separation was obtained with a total analysis time of less than 60 min, including the extraction-purification steps. Good responses for the six pyrethroids were obtained in a range of 50-500 μg L -1 , with linear coefficients higher than 0.9992. Instrumental limits of detection were between 0.22 and 0.63 μg L -1 , corresponding to 0.04 and 0.13 μg kg -1 in the matrix. Detection limits in chicken eggs and various meat samples, calculated on spiked samples, were in the range 0.05-0.25 μg kg -1 and 0.07-0.23 μg kg -1 , respectively. The validation results confirmed that the proposed GC-ECD method can be used as a reliable screening tool for the determination of pyrethroids in official check analyses. The method was extensively validated following the European directives, demonstrating its conformity in terms of selectivity, sensitivity, recovery, precision, and measurement uncertainty.

Pyrethrin I, pyrethrin II, cinerin I, cinerin II, jasmolin I and jasmolin II are six closely related insecticidal active esters, known as pyrethrins, found in the pyrethrum extract from the dry flowers of Tanacetum cinerariifolium. The chemical structures of the six compounds differ only in the terminal moieties at the acid and alcohol ends, but the compounds' in vivo toxicities are substantially different. Pyrethrins are lead compounds for pyrethroids, a large family of synthetic insecticides that alter nerve functions by prolonging the opening of voltage-gated sodium channels. However, data on the mechanism of action of natural pyrethrins are very limited. In this study, we examined the actions of all six pyrethrins on cockroach sodium channels expressed in Xenopus oocytes. Although the six compounds showed comparable potencies in inhibiting the inactivation of sodium channels, they had greatly variable potencies in inhibiting channel deactivation. Furthermore, unlike pyrethroids, the action of pyrethrins neither depend on nor were enhanced by repeated channel activation. We created a NavMs-based model of the cockroach sodium channel, in which pyrethrin II was docked at the pyrethroid receptor site 1 (PyR1), and proposed a rationale for the observed structure-activity relationship of the six pyrethrins. Our study sheds light on the molecular mechanism of pyrethrum action on sodium channels and reveled differences in the modes of action of the six bioactive constitutes of pyrethrum., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Ubiquitous presence of cypermethrin as a contaminant in surface stream and soil necessitates to develop potential bioremediation methods to degrade and eliminate this pollutant from the environment. A cypermethrin utilizing bacterial strain (MIC, 450  ppm) was isolated from the soil of pesticide contaminated agriculture field and characterized by using polyphasic approach. On molecular basis bacterial isolate showed 98% homology with Bacillus subtilis strain 1D. Under optimized growth conditions, bacteria showed 95% degradation of cypermethrin after 15 days and the end products of cypermethrin biodegradation under aerobic conditions were cyclododecylamine, phenol, 3-(2,2-dichloroethenyl 2,2-dimethyl cyclopropane carboxylate,1-decanol,chloroacetic acid, acetic acid, cyclopentan palmitoleic acid, and decanoic acid. Amplification of esterase (700 bp) and laccase (1200 bp) genes was confirmed by PCR which showed a possible role of these enzymes in biodegradation of cypermethrin. In the presence of cypermethrin Km value(s) of both the enzymes was low than the control. A nobel cypermethrin degradation pathway followed by B. subtilis was proposed on the basis of characterization of biodegraded products of cypermethrin using GC-MS. Cypermethrin biodegradation ability of Bacillus subtilis strain 1D without producing any toxic end product reveals the potential of this organism in cleaning of pesticide contaminated soil and water.

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, [P 44412 ]Br was used as a surfactant that could be removed from water via the addition of KPF 6 . 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, [P 44412 ]Br-to-KPF 6 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., (Copyright © 2018. Published by Elsevier B.V.)

The metal-organic framework [(La 0.9 Sm 0.1 ) 2 (DPA) 3 (H 2 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 [(La 0.9 Sm 0.1 ) 2 (DPA) 3 (H 2 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., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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, β-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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A polymer-based adsorption medium with molecular recognition ability for homologs of pyrethroids was prepared by atom transfer radical polymer iration using a fragment imprinting technique. Phenyl ether-biphenyl eutectic was utilized as a pseudo-template molecule, and the adsorption medium prepared was evaluated by solid-phase extraction and gas chromatography. Selectivity of the medium for pyrethroids was evaluated using it as solid phase extraction packing by Gas Chromatography. The results demonstrated that the absorption amount of bifenthrin, fenpropathrin, permethrin, cypermethrin, fenvalerate, Dursban and pentachloronitrobenzene for molecularly imprinted polymers were 2.32, 2.12, 2.18, 2.20, 2.30, 1.30 and 1.40mgg -1 , respectively, while the non-imprinted polymers were 1.20, 1.13, 1.25, 1.05, 1.20, 1.23 and 1.32mgg -1 , respectively. The rebinding test based on the molecularly imprinted solid phase extraction column technique showed the recoveries of honey sample spiked with seven insecticides within 88.5-106.2%, with relative standard deviations of 2.38-5.63%. Finally, the method was successfully applied to the analysis of pyrethroids in a honey sample., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Covalent organic frameworks (COFs), as an emerging class of crystalline porous organic polymers, have great potential for applications in chromatographic separation owning to their fascinating crystalline structures and outstanding properties. However, development of COF materials as novel stationary phases in high performance liquid chromatography (HPLC) is just in its infancy. Herein, we report the design and construction of a new hydrazone-linked chiral COF, termed BtaMth COF, from a chiral hydrazide building block (Mth) and present a one-pot synthetic method for the fabrication of BtaMth@SiO 2 composite for HPLC separation of isomers. The as-synthesized BtaMth chiral COF displays good crystallinity, high porosity, as well as excellent chemical stability. Meanwhile, the fabricated HPLC column by using BtaMth@SiO 2 composite as the new stationary phase exhibits high resolution performances for the separation of positional isomers including nitrotoluene and nitrochlorobenzene, as well as cis-trans isomers including beta-cypermethrin and metconazole. Additionally, some effects such as the composition of the mobile phase and column temperature for HPLC separations on the BtaMth@SiO 2 packed column also have been studied in detail. The successful applications indicate the great potentials of hydrazone-linked chiral COF-silica composite as novel stationary phase for the efficient HPLC separation., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A high-surface-area nanoporous carbon (NPC) has been successfully synthesized by using the metal-organic framework ZIF-90 as both the template and precursor together with furfuryl alcohol as a secondary carbon source. The prepared ZIF-90 templated NPC (ZIF-90-NPC) was then coated onto a stainless steel wire by a simple physical adhesion approach to prepare solid-phase microextraction (SPME) fiber. By coupling the ZIF-90-NPC coated fiber-based SPME with gas chromatography-microelectron capture detection (GC-μECD), the developed method gave a large enhancement factor (984-2869), low limit of detection (0.1-0.5ngg -1 ) and good linearity (0.3-50ngg -1 ) for the determination of some pyrethroid pesticides (bifenthrin, fenpropathrin, cyhalothrin, permethrin, cyfluthrin, flucythrinate, fenvalerate and deltamethrin) from different fruits and vegetables. The relative standard deviations (RSDs) for six replicate extractions of the pyrethroids by the ZIF-90-NPC coated fiber ranged from 4.3% to 8.0%. The recoveries of the spiked pyrethroids (5ngg -1 and 20ngg -1 ) from fruit and vegetable samples were in the range of 88.0-104.0% and 86.0-103.5% with the RSDs ranging from 4.8% to 12.9% and 5.0-10.8%, respectively. Besides, the ZIF-90-NPC coated fiber was stable enough for 100 extraction cycles without a significant loss of extraction efficiency. The method was successfully applied to the determination of the pyrethroids in fruit and vegetable samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

As a natural and healthy beverage, tea is widely enjoyed; however, the pesticide residues in tea leaves affect the quality and food safety. To develop a highly selective and efficient method for the facile removal of pesticide residues, the subcritical butane extraction (SBE) technique was employed, and three variables involving temperature, time and extraction cycles were studied. The optimum SBE conditions were found to be as follows: extraction temperature 45 °C, extraction time 30 min, number of extraction cycles 1, and in such a condition that the extraction efficiency reached as high as 92%. Further, the catechins, theanine, caffeine and aroma components, which determine the quality of the tea, fluctuated after SBE treatment. Compared with the uncrushed leaves, pesticide residues can more easily be removed from crushed leaves, and the practical extraction efficiency was 97%. These results indicate that SBE is a useful method to efficiently remove the bifenthrin, and as appearance is not relevant in the production process, tea leaves should first be crushed and then extracted in order that residual pesticides are thoroughly removed.

Use of Tenax extractable concentrations to estimate biological exposure to hydrophobic organic contaminants is well documented, yet method variation exists between studies, specifically in the ratio of Tenax mass to organic carbon mass in the sediment (Tenax:OC ratio) being extracted. The effects of this variation on exposure estimates are not well understood. As Tenax is theoretically in direct competition with organic carbon for freely dissolved chemical in sediment interstitial water, varying the Tenax:OC ratio could impact single-point Tenax extraction (SPTE) exposure estimates. Therefore, the effects of varying Tenax:OC ratios on SPTE pyrethroid concentrations from field-contaminated and laboratory-spiked sediments were compared to bioaccumulation by Lumbriculus variegatus. The Tenax:OC ratio had minimal effect on SPTE pyrethroid concentrations. The SPTE pyrethroid concentrations obtained using the highest and lowest Tenax:OC ratios ranged from 0.85- to 3.91-fold different, which is unlikely to contribute substantial error to bioaccessibility estimates. Comparisons to Tenax exposure endpoints from previous research reveal the variation in these endpoints is likely due to toxicokinetic and toxicodynamic differences; processes common to exposure estimates provided by any chemical extraction technique. As the pyrethroid concentrations in the experimental sediments caused toxicity to L. variegatus, thus affecting bioaccumulation, the SPTE concentrations overestimated bioaccumulation. However, SPTE concentrations strongly correlated with growth inhibition regardless of the Tenax:OC ratio, providing accurate estimates of the correct exposure endpoint. Tenax masses of 0.500-0.800 g should provide sufficient Tenax to achieve Tenax:OC ratios of at least 5:1, which will provide accurate exposure estimates while retaining the ease of conducting SPTEs., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

An on-site dispersive liquid liquid microextraction base on the solidification of switchable solvent has been developed as a simple, rapid and eco-friendly sample extraction method for the fast determination of pyrethroid insecticides in aqueous samples using high-performance liquid chromatography with ultraviolet detection. In this extraction method, medium-chain saturated fatty acids (n≥10), which can rapidly solidify at low temperatures (<20°C), were investigated as switchable hydrophilic solvents. The fatty acids were converted into the hydrophilic form by adding sodium hydroxide. Microdroplets of the fatty acids were generated when injected into an acidic sample that had been pretreated by the addition of sulfuric acid. The formed cloudy solution was cooled to a low temperature to turn the fatty acids into a solid, which was then separated by filtration, thus avoiding the time-consuming step of centrifugation. The microextraction process was performed in a 10mL syringe and the pretreatment process could thus be finished in 5min. No external energy resources were required in this method, which makes it a potential method for on-site extraction. The optimal experimental parameters were as follows: 350μL of decanoic acid (1mol/L) was used as the extraction solvent, 150μL of sulfuric acid (2mol/L) was used to decrease the pH of the samples, no salt was added, and the temperature of the samples was in the range of 20-40°C. Finally, the sample was cooled in an ice bath for three minutes. Under these optimal conditions, good responses for four pyrethroid insecticides were obtained in the concentration ranges of 1-500μg/L, with coefficients of determination greater than 0.9993. The recoveries of the four pyrethroid insecticides ranged from 84.7 to 95.3%, with relative standard deviations ranging from 1.6 to 4.6%. The limits of detection based on a signal-to-noise ratio of 3 were in the range of 0.24-0.68μg/L, and the enrichment factors were in the range of 121-136. The results demonstrate that this method was successfully applied to determine pyrethroid insecticides in real water samples. No centrifugation or any special apparatus are required, make this a promising method for rapid field-sampling procedures., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This study aimed to develop an efficient, sensitive, and reliable analytical method for trace analysis of 17 different pyrethroids and chlorpyrifos in the fatty content of animal products, including beef, chicken, eggs, fish, and milk. The method developed is based on an ultrasound extraction using lyophilized samples, a solid phase extraction cleanup with basic alumina and C18 cartridges in tandem, and analysis by gas chromatography coupled to tandem mass spectrometry in negative chemical ionization mode. Recovery values were in the range of 27-128 % with relative standard deviation always below 25 %, and chiral analysis of recovery data showed predominance of isomers of cis form over trans. Limits of detection (LODs) ranged from 0.002 to 6.43 ng g -1 lipid weight (lw), and limits of quantification (LOQs) ranged between 0.006 and 21.4 ng g -1  lw. The developed methodology was used for the analysis of 25 samples of fatty foods. All samples were positive for at least one of the pesticides, chlorpyrifos, bifenthrin, cyhalothrin, permethrin, cypermethrin, or deltamethrin, with mass fraction levels ranging from 0.03 to 270 ng g -1 lw. Graphical Abstract ᅟ.

Pyrethrum is a natural insecticide extracted from Tanacetum cinerariifolium. Six esters, the pyrethrins, are responsible for the extract's insecticidal activity. The oxidative degradation of pyrethrins through contact with aerial oxygen is a potential cause of pyrethrin losses during pyrethrum manufacture. Described here is the first investigation of the autoxidation chemistry of the six pyrethrin esters isolated from pyrethrum. It was found that pyrethrins I and II, the major pyrethrin esters present in pyrethrum, undergo autoxidation more readily than the minor pyrethrin esters, the jasmolins and cinerins. Chromatographic analysis of pyrethrin I and II autoxidation mixtures showed some correlation with a similar analysis performed on extracts from T. cinerariifolium crop, which had been stored for 12 weeks without added antioxidants. Two pyrethrin II autoxidation products were isolated, characterized, and shown to be present in extracts of stored T. cinerariifolium crop, confirming that autoxidation of pyrethrin esters does occur during crop storage.

Objective: To establish a method for simultaneous determination of chlorfenapyr and indoxacarb in tea by gas chromatography-mass spectrometry., Methods: The tea samples were homogenized and extracted with acetonitrile. Extracts obtained through centrifugation were cleaned up by CARB / NH2 cartridges, and further purified with SLH cartridges. After separated by DB-5MS capillary column( 30 m × 0. 25 mm × 0. 25μm), the analytes were measured by gas chromatography-mass spectrometry in selective ion monitoring( SIM) mode and quantified by external standard method., Results: The linear range was 0. 10- 10 μg / m L for both of the two pesticides. The detection limits of chlorfenapyr and indoxacarb in tea samples were 0. 01 and 0. 008 mg / kg, and the quantitation limits were 0. 03 and 0. 025 mg / kg, respectively. The recoveries were from75. 6% to 92. 7%, and the relative standarddeviations( RSDs) were 3. 6%- 11. 4%( n =6)., Conclusion: The proposed method has good purification effect and high accuracy, which is capable for simultaneously detecting the chlorfenapyr and indoxacarb in tea samples.

We designed a novel hydrazone covalent organic framework (COF) and developed a polydopamine (PDA) method to immobilize COF on a stainless steel fiber for headspace solid-phase microextraction (HS-SPME). A series of characterization studies was performed to validate the structure and property of the prepared fiber. The COF-PDA fiber was applied for the extraction of pyrethroids coupled with gas chromatography equipped with an electron capture detector (GC-ECD). Under the optimum experimental conditions, high enhancement factors of 307-2327 were achieved, indicating that the hydrazone COF possessed good extraction efficiency for pyrethroids. The detection limits ranged from 0.11 to 0.23μgkg(-1) with relative standard deviations varying in the range of 3.6-9.2% (intra-batch) and 6.9-12.1% (inter-batch), respectively. The developed method was applied to the determination of pyrethroids in fruit and vegetable samples and the accuracy was assessed through recovery experiments., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Pyrethroid insecticides are used extensively in agriculture, and they, as well as their environmental degradates, may remain as residues on foods such as fruits and vegetables. Since pyrethroid degradates can be identical to the urinary markers used in human biomonitoring, it is important to understand the contribution of these degradates when studying sources of human pyrethroid exposure. We modified the widely used Quick Easy Cheap Effective Rugged Safe (QuEChERS) method to measure several current-use pyrethroids (cis/trans-permethrin, cypermethrin, deltamethrin, esfenvalerate, bifenthrin, cyfluthrin, and cyhalothrin) and their environmental degradation products (3-PBA, cis/trans-DCCA, 4-F-3-PBA, DBCA, and MPA) in selected fresh fruits and vegetables. Using fortified samples, we determined extraction efficiencies from: tomatoes, oranges (whole, peeled, and rind), grapes, apples, bananas (peeled and rind only), onions, lettuce, green peppers, carrots and broccoli. For a subset of these food items (apples, grapes, tomatoes, lettuce and banana peel), we also established limits of detection (MDLs) and quantitation (MQLs). Each sample was homogenized (1kg) then spiked with the target pyrethroids and their degradation products. Sub-samples (15g) were extracted with acetonitrile, then salted out and partitioned with NaCl and MgSO4. The extract was divided and further cleaned using solid phase extraction (SPE) cartridges containing either graphitized non-porous carbon (pyrethroids) or C18 (degradation products). Sample analysis was via liquid chromatography/tandem mass spectrometry (LC-MS/MS). Considering the mean recoveries each of the 14 analytes in all 13 matrices: 42% of the recoveries were ≥90%, 70% were ≥80%, and 90% were ≥70%. All MDL's were less than 100ng/kg, except 3-PBA (132ng/kg, tomato), MPA (129ng/kg, tomato), and trans-permethrin (141ng/kg, banana peel). We then applied the method to non-spiked samples (subset of 5 for which the MDLs/MQLs had been determined) collected weekly for four weeks from local supermarkets. At least one pyrethroid was present in measureable concentrations in all matrices except banana peels. In contrast, the only degradation products detected were cis/trans-DCCA, in one lettuce sample., (Published by Elsevier B.V.)