Sensitive extraction of seven pesticide residues from environmental water with magnetic graphene oxide-based covalent organic framework.

The use of pesticides has increased with the development of agriculture. However, due to the trace content and the matrix's inherent complexity in environmental water, development of rapid and sensitive detection method present significant challenges in the analysis of pesticide residues. The study synthesized magnetic graphene oxide (MGO) by combining superparamagnetic nanoparticles with the easy modification of graphene oxide (GO). Covalent organic frameworks (COFs) were then modified to have a large specific surface area. Finally, magnetic graphene oxide-based covalent organic frameworks, namely MGO-COFs, were obtained with a spherical structure and used as magnetic solid-phase extraction materials, which was successfully used to determine the seven pesticide residues in environmental samples in conjunction with high performance liquid chromatography. The method has a wide linear range for the tested pesticides, with satisfactory correlation coefficients (R ≥ 0.099) and low detection limits (0.3-1.21 µg L-1). The correlation coefficients for all seven pesticides were high (R2 ≥ 0.9996). The spiked recoveries, exhibiting a range of 91.3 to 109 %, demonstrated that the developed MGO-COF-MSPE-HPLC-UV method is simple, efficient, and suitable for the analysis and detection of seven pesticide residues in environmental water.

Reduced graphene oxide decorated NiCo2(OH)6 nanoflowers for vortexed assisted dispersive µ-solid-phase extraction of organophosphorus pesticides in baby food cereal, rice and wheat flour.

Food safety is an important issue to protect humane health and improve the life quality. Hence, analysis of the possible contaminants in food samples is essential. A rapid and efficient vortexed-assisted dispersive µ-solid-phase extraction coupled with gas chromatography-mass spectrometry was proposed for simultaneous separation/preconcentration and determination of five commonly used organophosphorus pesticides. Reduced graphene oxide decorated NiCo2(OH)6 nanoflowers as a novel nanostructure was synthetized and introduced for separation of the target pesticides from the wheat flour, rice flour, and baby food cereal samples. The characterization of the nanoflowers was accomplished by SEM-EDX, XRD, and FT-IR techniques. The main factors including pH, the amount of nanoflower, the volume of sample solution, salt concentration (ionic strength), desorption conditions (i.e. desorption solvent type and volume, and desorption time) on the pesticides extraction efficiencies were inquired using matrixed match method. Applying the optimum conditions, the linearity of 0.100-500.000 µg kg-1, LODs and LOQs in the range of 0.03-0.04 µg kg-1 and 0.1 µg kg-1 for the studied food samples were obtained. The repeatability (intra-day precision (n = 5)) of ≤ 2.0 % and reproducibility (inter-day precision, days = 5, n = 3) of ≤3.1 % and were appraise at three concentration levels (10, 50 and 100 µg kg-1 of each analyte). High relative recoveries of 90.0-99.3 % ascertained high potential of the presented method for complex matrix analysis.

Hexafluoroisopropanol-based supramolecular solvent for liquid phase microextraction of pesticides in milk.

Residues of pesticides in milk may pose a threat to human health. This study aimed to develop a liquid-phase microextraction (LPME) method using hexafluoroisopropanol (HFIP)-based supramolecular solvent (SUPRAS) for the simultaneous extraction and purification of four pesticides (boscalid, novaluron, cypermethrin and bifenthrin) in milk. Pesticides were extracted using SUPRAS prepared with nonanol and HFIP, and the extraction efficiency was analyzed. Results showed satisfactory recoveries ranging from 80.8%-111.0%, with relative standard deviations (RSDs) of <6.4%. Additionally, satisfactory linearities were observed, with correlation coefficients >0.9952. The limits of quantification (LOQs) were in the range of 1.8 µg·L-1-14.0 µg·L-1. The established method demonstrated high extraction efficiency with a short operation time (15 mins) and low solvent consumption (2.7 mL). The HFIP-based SUPRAS LPME method offers a convenient and efficient approach for the extraction of pesticides from milk, presenting a promising alternative to conventional techniques.

Covalent organic framework-functionalized magnetic MXene nanocomposite for efficient pre-concentration and detection of organophosphorus and organochlorine pesticides in tea samples before gas chromatography-triple quadrupole mass spectrometry analysis.

In this study, a hydrophobic covalent organic framework-functionalized magnetic composite (CoFe2O4@Ti3C2@TAPB-TFTA) with a high specific area with 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 2,3,5,6-tetrafluoroterephthalaldehyde (TFTA) was designed and synthesized through Schiff base reaction. An efficient magnetic solid-phase extraction method was established and combined with gas chromatography-triple quadrupole mass spectrometry to sensitively determine 10 organochlorine and organophosphorus pesticides in tea samples. The established method exhibited good linearity in the range of 0.05-120 µg/L and had low limits of detection (0.013-0.018 µg/L). The method was evaluated with tea samples, and the spiked recoveries of pesticides in different tea samples reached satisfactory values of 85.7-96.8%. Moreover, the adsorption of pesticides was spontaneous and followed Redlich-Peterson isotherm and pseudo-second-order kinetic models. These results demonstrate the sensitivity, effectiveness, and reliability of the proposed method for monitoring organochlorine and organophosphorus pesticides in tea samples, providing a preliminary basis for researchers to reasonably design adsorbents for the efficient extraction of pesticides.

Multi-residue determination of biocides in dairy products and slurry feed using QuEChERS extraction and liquid chromatography combined with high resolution mass spectrometry (LC-ESI-QOrbitrap™-MS).

Given that the determination of biocides in food and feed is currently not routinely done, more information on these compounds is useful for consumer's safety. This work describes a sensitive and reliable method for quantitative analysis of a wide range of biocides in dairy products and slurry feed. The method comprises acetate-buffered QuEChERS extraction without clean-up. Analyses were performed by LC-Q-Orbitrap™-MS and a full-scan acquisition event without fragmentation was followed by five fragmentation events (data-independent acquisition-DIA). The quantitative validation was performed according to SANTE/11312/2021 at 10, 50 and 200 ng g-1 spiking levels, and the results showed that the vast majority of the compounds met the criteria for trueness and precision. The LOQ was 10 ng g-1 for the majority of biocides depending on the matrix. The method was successfully applied to quantify biocides in dairy products and feed.

Evaluating the effectiveness of different household washing techniques for removal of insecticides from spinach and chickpea leaves by micellar liquid chromatography.

In the past few decades, the employment of green analytical approaches in chromatographic method development has attracted the analytical separation community. The greenness of the developed method depends upon the toxicity of solvents and the amount of generated post-analysis waste generated. In this concern, micellar liquid chromatography (MLC) is a simple and rapid technique that generates very low toxic waste compared to traditional chromatographic pesticide detection methods. Here, MLC method has been validated and applied for the determination of monocrotofos (MCF), imidacloprid (ICP), dimethoate (DM) and profenofos (PFF) in spinach and chickpea leaves. The optimized mobile phase was 0.065 M SDS-2 % 1-propanol, 0.01 M NaH2PO4 buffered to pH 7. A C18 column was used for separation with a flow rate of 1 mL/min. The developed method has been validated following the guidelines of SANTE/11,312/2021 and ICH guidelines for; limit of quantification (0.05-0.20 mg/kg), linearity (r2> 0.997-0.999), precision (<6.3 %), accuracy (96.3 %-99.8 %) and robustness (<6) in real samples. ICP and MCF, apart from DM and PFF, were detected in the present work. After detecting insecticides in spinach and chickpea leaves both were washed with different household chemicals i.e. normal, lukewarm, common salt, lemon juice water and commercial ozonizer. Based on five washing techniques with insecticide concentration time intervals reduction rates were calculated for each washing treatment. The results show that lemon juice, common salt water, and ozonizer can be used as washing techniques for the reduction of superficial and systematic residues of ICP and MCF. Common salt and lemon juice water were better for washing over vinegar and potassium permanganate (KMnO4) as they enhance the colour of the green leafy vegetables and are available in every Indian kitchen. They can be easily used by lower socioeconomic classes who cannot afford KMnO4 and vinegar.

In vivo tracing of cyromazine and three neonicotinoids in cowpea under field conditions by solid-phase microextraction combined with ultra-performance liquid chromatography-tandem mass spectrometry.

BACKGROUND: Excessive pesticide residues in agricultural products could accumulate in organisms through the food chain, causing potential harm to human health. The investigation of dissipation kinetics and residues of pesticides in crops is crucial for the scientific application of pesticides and the mitigation of their adverse effects on human health. In vivo solid-phase microextraction (in vivo SPME) has unique advantages, but the research on field plants is still lacking and the quantitative correction methods need to be further developed. RESULTS: A method combining in vivo solid-phase microextraction with ultra-performance liquid chromatography-tandem mass spectrometry (in vivo SPME-UPLC-MS/MS) was developed to monitor the presence of acetamiprid, cyromazine, thiamethoxam and imidacloprid in cowpea fruits grown in the field. The sampling rates (Rs) were determined using both in vitro SPME in homogenized cowpea samples and in vivo SPME in intact cowpea fruit samples. The in vivo-Rs values were significantly higher than the in vitro-Rs for the same analyte, which were used for in vivo SPME correction. The accuracy of this method was confirmed by comparison with a QuEChERS-based approach and subsequently applied to trace pesticide residues in field-grown cowpea fruits. The residual concentrations of each pesticide positively correlated with application doses. After 7 days of application at two different doses, all of the pesticides had residual concentrations below China's maximum residue limits. Both experimental data and predictions indicated that a safe preharvest interval for these pesticides is 7 days; however, if the European Union standards are to be met, a safe preharvest interval for cyromazine should be at least 13 days. SIGNIFICANCE: This study highlights the advantages of in vivo SPME for simultaneous analysis and tracking of multiple pesticides in crops under field conditions. This technique is environmentally friendly, minimally invasive, highly sensitive, accurate, rapid, user-friendly, cost-effective, and capable of providing precise and timely data for long-term pesticide surveillance. Consequently, it furnishes valuable insights to guide the safe utilization of pesticides in agricultural production.

Determination of pesticide residues in soybeans using QuEChERS followed by deep eutectic solvent-based DLLME preconcentration prior to gas chromatography-mass spectrometry analysis.

A reliable and greener alternative to the usual extraction methods is reported for the determination of pesticide residues in soybeans. This novel approach combines the classical QuEChERS extraction method with a DLLME (dispersive liquid-liquid microextraction) step, utilizing a deep eutectic solvent (DES) - camphor: hexanoic acid (1:1 molar ratio) - as the microextraction solvent. This DES has never been employed in pesticide analysis by gas chromatography-mass spectrometry of complex matrices like soybeans. A Plackett-Burman screening design was employed to optimize sample preparation variables of QuEChERS (amount of sodium chloride and magnesium sulfate, and amount of PSA and C18 sorbents) and DLLME (pH of medium, amount of sodium chloride, and volume of microextraction solvent). This design allowed for a systematic evaluation of the impact of each parameter on the method's performance. The optimized method was evaluated using a certified reference material and commercial samples of soybeans. The method exhibited high accuracy and precision for most of the analytes under study, demonstrating its applicability for pesticide residue analysis in soybeans. To assess the greenness and practicality of the developed method, the Analytical Greenness (AGREE) and Blue Applicability Grade Index (BAGI) metric systems were employed, respectively. Overall, the proposed QuEChERS-DLLME method using a DES solvent is a reliable and greener alternative to conventional extraction methods for the determination of pesticide residues in soybeans. Its high performance, coupled with its environmental friendliness, makes it a promising tool for food safety analysis.

Metal-organic framework-based aptasensor utilizing a novel electrochemiluminescence system for detecting acetamiprid residues in vegetables.

The work was based on N-(4-Aminobutyl)-N-ethylisoluminol (ABEI)-functionalized Fe-MIL-101 and gold nanoparticles (AuNPs) as sensing materials, and an electrochemiluminescence (ECL) aptasensor was constructed for detecting acetamiprid. As a metal-organic framework (MOF) material, Fe-MIL-101, was renowned for its unique three-dimensional network structure and efficient catalytic capability. ABEI, a common ECL reagent, was widely applied. ABEI was introduced into the Fe-MIL-101 structure as a luminescence functionalization reagent to form Fe-MIL-101@ABEI. This approach avoided limitations on the loading capacity of luminescent reagents imposed by modification and encapsulation methods. With character of excellent catalytic activity and ease of bioconjugation, AuNPs offered significant advantages in biosensing. Leveraging the reductive properties of ABEI, AuNPs were reduced around Fe-MIL-101@ABEI, resulting in the modified luminescent functionalized material denoted as Fe-MIL-101@ABEI@AuNPs. An aptamer was employed as a recognition element and was modified accordingly. The aptamer was immobilized on Fe-MIL-101@ABEI@AuNPs through gold-sulfur (Au-S) bonds. After capturing acetamiprid, the aptamer induced a decrease in the ECL signal intensity within the ABEI-hydrogen peroxide (H2O2) system, enabling the quantitative detection of acetamiprid. The aptasensor displayed remarkable stability and repeatability, featured a detection range of 1×10-3-1×102 nM, and had a limit of detection (LOD) of 0.3 pM (S/N=3), which underscored its substantial practical application potential.

Determination of insecticide residues in beverages based on MIL-100(Fe) dispersive solid-phase microextraction in combination with dispersive liquid-liquid microextraction followed by HPLC-MS/MS.

A novel dispersive solid-phase microextraction method based on a metal-organic framework (MIL-100(Fe)) combined with a dispersive liquid-liquid microextraction technique was proposed for the extraction and enrichment of four insecticides in beverages. The qualitative and quantitative analysis of these insecticides was conducted using HPLC-MS/MS. To optimize the extraction process, several parameters were investigated, and the main variables were optimized using CCD-based RSM. The developed method displayed a wide linear range of 1.000-1000 ng/L and R2 values >0.993 for all four calibration curves. The method demonstrated high sensitivity, with LODs and LOQs of 0.3-0.6 ng/L and 0.8-1.0 ng/L, respectively. In addition, the greenness of the proposed method was assessed using the Complex GAPI tool, and the results showed that the proposed method exhibits benefits, such as minimal usage of organic solvents and negligible matrix influence, making it a suitable method for the detection of insecticide residues in beverages.

Determination of twelve neonicotinoid pesticides in chili using an improved QuEChERS method with UPLC-Q-TOF/MS.

In this study, a QuEChERS method based on citrate was developed and utilized for the analysis of twelve neonicotinoid pesticides in fresh red chilies, fresh green chilies, and dried chilies, coupled with ultra-high performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF/MS). In the sample preparation, acetonitrile containing 1% formic acid was used as the extraction solvent. Anhydrous sodium sulfate replaced the traditional anhydrous magnesium sulfate for water removal, effectively eliminating the issues of salt caking. Graphitized carbon black, octadecyl silica, and primary secondary amine were used as cleaning agents. The method showed good sensitivity, with the limits of quantification below 0.03 mg/kg for fresh chilies and below 0.15 mg/kg for dried chilies. Values of matrix effects ranged from -19.5% to 8.4%, and the recovery was 86.9% - 105.2%. The analytical method provided an effective tool for the high throughput detection of neonicotinoid pesticide residues in multiple chili matrices.

COF-SiO2@Fe3O4 Composite for Magnetic Solid-Phase Extraction of Pyrethroid Pesticides in Vegetables.

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-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 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-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.

Etched stainless steel wire modified with conjugated microporous polymers-F6 for jacket-free stir bar sorptive extraction of benzoylureas in juice sample.

Benzoylurea (BU) insecticides have been widely used for pest control as third-generation insecticides. Considering that their residues in food may cause adverse effects on human health, the upper limits of BUs remaining in food have been set by the administration. Therefore, it is essential to develop a sensitive and efficient analytical method to determine the residues of BUs in food. Stir bar sorptive extraction (SBSE) is a novel sample preparation technique, and stainless steel wire (SSW) is an ideal substrate for an SBSE device. In this work, a novel SBSE device of SSW jacket-free stir bar with a dumbbell shape was designed and prepared. The conjugated microporous polymer CMP-F6, which possesses a porous structure, high hydrophobicity and rich fluorine-containing functional groups, was immobilized on the surface of SSW by the method of polyacrylonitrile glue adhesion. Compared with previous studies, which used SSW as a substrate, the method of etching partial SSW with hydrochloric acid, on the one hand, made the surface of SSW rough and easy to modify the extraction coating, and on the other hand, converted itself into a dumbbell-shaped structure, which is conducive to improving the extraction efficiency and stability of the SBSE device. The method of SBSE-HPLC-UV was established for determining five BUs. Owing to the hydrophobic interaction and F-F interaction between CMP-F6 and analytes, this method showed good extraction efficiency and had good linearity (R2 ≥ 0.9945) and high sensitivity (LODs in the range of 0.1-0.2 ng mL-1). It was used for the analysis of benzoylurea in an apple juice sample, and the recoveries were 74.3-117.9%.

The pesticide residue analysis in commodities with high content of chlorophyll based on the quick, easy, cheap, effective, rugged, and safe method: A review.

In multiresidue analysis, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) is one of the most popular techniques routinely used by researchers during pesticide analysis of food and vegetable samples. Originally, the QuEChERS method was developed for analysis of pesticide residues from fruits and vegetables, but rapidly gained popularity in the extraction of analytes from different matrices. This analytical approach shows several advantages over traditional extraction techniques: it requires lower sample and solvent amounts while shortening the time of sample preparation. However, it presents some limitations for complex matrices such as those containing high amounts of chlorophyll. To overcome the problem of strong matrix effect and influence of interferences, different approaches are applied. Most are concerning modifications of the cleanup step, that is, sorbent type and its amount. Optimization of other parameters, such as sample size, hydration level, extraction solvent, and buffering, also has an impact on overall performance. Combining proper sample preparation with modern highly sensitive and selective detection techniques enables receiving desired limits of quantification. This article presents an overview of strategies employed by researchers for analysis of green, high chlorophyll content commodities and results obtained in their studies.

Smartphone-based molecularly imprinted sensors for rapid detection of thiamethoxam residues and applications.

In order to achieve rapid detection of thiamethoxam residues in mango, cowpea and water, this study modified the screen printed carbon electrode (SPCE) to make a specific molecular imprinting sensor (Thiamethoxam-MIP/Au/rGO/SPCE) for thiamethoxam. An integrated smartphone platform was also built for thiamethoxam residue analysis. The performance of the complete system was analyzed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The system was then applied for the rapid determination of thiamethoxam residues in water, mango and cowpea samples. The results showed that the molecular sensor showed good linearity in the range 0.5-3.0 µmol/L of thiamethoxam. The detection limit of thiamethoxam was 0.5 µmol/L. Moreover, the sensor had good reproducibility and anti-interference performance. The average recovery rates of the pesticide residues in water, mango and cowpea samples were in the range of 90-110% with relative standard deviations < 5%. The rapid detection system for thiamethoxam residue constructed in this study was simple, reliable, reproducible and had strong anti-interference. It has broad application prospects in the field detection of thiamethoxam residue, and serves as a valuable reference for the further development of rapid detection technology of pesticide residues in the field of environment and food safety.

Fatty Acid Analysis, Chemical Constituents, Biological Activity and Pesticide Residues Screening in Jordanian Propolis.

Propolis is a resinous natural product collected by honeybees (Apis mellifera and others) from tree exudates that has been widely used in folk medicine. The present study was carried out to investigate the fatty acid composition, chemical constituents, antioxidant, and xanthine oxidase (XO) inhibitory activity of Jordanian propolis, collected from Al-Ghour, Jordan. The hexane extract of Jordanian propolis contained different fatty acids, which are reported for the first time by using GC-FID. The HPLC was carried out to identify important chemical constituents such as fatty acids, polyphenols and α-tocopherol. The antioxidant and xanthine oxidase inhibitory activities were also monitored. The major fatty acid identified were palmitic acid (44.6%), oleic acid (18:1∆9cis, 24.6%), arachidic acid (7.4%), stearic acid (5.4%), linoleic acid (18:2∆9-12cis, 3.1%), caprylic acid (2.9%), lignoceric acid (2.6%), cis-11,14-eicosaldienoic acid (20:2∆11-14cis, 2.4%), palmitoleic acid (1.5%), cis-11-eicosenoic acid (1.2%), α-linolenic acid (18:3∆9-12-15cis, 1.1%), cis-13,16-docosadienoic acid (22:2∆13-16cis, 1.0%), along with other fatty acids. The major chemical constituents identified using gradient HPLC-PDA analysis were pinocembrin (2.82%), chrysin (1.83%), luteolin-7-O-glucoside (1.23%), caffeic acid (1.12%), caffeic acid phenethyl ester (CAPE, 0.79%), apigenin (0.54%), galangin (0.46%), and luteolin (0.30%); while the minor constituents were hesperidin, quercetin, rutin, and vanillic acid. The percentage of α-tocopherol was 2.01 µg/g of the lipid fraction of propolis. Antioxidant properties of the extracts were determined via DPPH radical scavenging. The DPPH radical scavenging activities (IC50) of different extracts ranged from 6.13 to 60.5 µg/mL compared to ascorbic acid (1.21 µg/mL). The xanthine oxidase inhibition (IC50) ranged from 75.11 to 250.74 µg/mL compared to allopurinol (0.38 µg/mL). The results indicate that the various flavonoids, phenolic compounds, α-tocopherol, and other constituents which are present in propolis are responsible for the antioxidant and xanthine oxidation inhibition activity. To evaluate the safety studies of propolis, the pesticide residues were also monitored by LC-MS-MS 4500 Q-Trap. Trace amounts of pesticide residue (ng/mL) were detected in the samples, which are far below the permissible limit as per international guidelines.

Residual characteristics of etofenprox in the processing stages of rice cakes and cookies.

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.

[Hydrophilic interaction liquid chromatography for removal of pesticide residues in ginseng extracts].

Ginseng extracts are rich in a variety of ginseng monomer saponins, which have pharmacological functions of retarding aging, enhancing immunity, stimulating blood circulation, and lowering blood pressure. Ginseng is widely used in health products and dietary supplements in the domestic and foreign market. However, the amount of pesticide residues is an important index for measuring the quality of ginseng and ginseng extracts. Therefore, studies focused on methods for the removal of pesticide residues in ginseng extract are of great significance. Hydrophilic interaction liquid chromatography (HILIC) is used to improve the retention and separation selectivity of strongly polar substances, and it is widely employed in drug analysis, metabolomics, proteomics, etc. In this study, a method for the removal of pesticide residues was developed based on the difference in the retention behavior of pesticide residues and ginsenosides on the HILIC column. Using commercially available ginsenoside extracts, the retention behaviors of pesticide residues and ginsenosides on reverse chromatography and hydrophilic chromatographic columns were evaluated by high performance liquid chromatography. The results proved that on the reversed-phase liquid chromatography (RPLC) stationary phase, in addition to the strong retentions of quintozene and pentachloroaniline, which could be clearly separated from the saponins, the retentions of the other five pesticide residues including carbendazim, azoxystrobin, procymidone, iprodione and propiconazole were similar to total ginsenosides. The seven ginsenosides showed strong retention due to the formation of hydrogen bonds between the hydroxyl groups on the sugar chain and the carboxyl groups on the HILIC stationary phase. However, the pesticide residues were not well retained because of their poor hydrophilicity and small molecular weights. For this reason, the pesticide residues and ginsenosides could be completely separated on the HILIC column. Thus, enrichment of the seven ginsenosides and removal of the 14 pesticide residues was realized in one step on the HILIC column. In addition, the effects of loading amount, loading volume, and washing volume on the removal of pesticide residues in ginsenosides were investigated using the Click XIon SPE column. Then, taking the ginsenoside recoveries and pesticide residue removal rates into account, we confirmed the following: the ratio of the maximum sample loading mass to the filler mass was 1∶10; the optimal elution volume was twice the column volume; and the optimal loading volume was twice the column volume. The ginseng extracts were solvated with a 95% ethanol solution and loaded onto an HILIC column. The sample was subjected to pesticide residue removal, and ginsenoside purification and enrichment under the optimum removal conditions. Gradient elution was carried out using ethanol and water as the mobile phases. The total ginsenoside content in the final extracts was increased to 69.61%. The recovery of the total ginsenosides was 94.4%. The pesticide residues in the samples were quantitatively detected by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) in the multiple reaction monitoring (MRM) mode. The 14 pesticide residues in the original ginsenoside extracts were effectively removed. The amounts of five residues were reduced to below 0.05 mg/kg, while the other nine residues were completely eliminated. This study demonstrates the application of HILIC to pesticide residue removal in traditional Chinese medicine extracts and reveals a new technique for the purification of natural products. The proposed method shows a high removal rate of pesticide residues and a high recovery of total ginsenosides. It is safe, efficient, and environment-friendly, and can aid the development of high-quality ginsenoside extracts.

A fluorinated chitosan-based QuEChERS method for simultaneous determination of 20 organophosphorus pesticide residues in ginseng using GC-MS/MS.

In this study, a new fluorinated methacrylamide (MACF) was synthesized and evaluated as an adsorbent in the dispersive solid-phase extraction for the effective determination and extraction of 20 organophosphorus pesticides (OPPs) from ginseng samples using the QuEChERS (quick, easy, cheap, effective, rugged, safe) method coupled with GC-MS/MS. The properties of MACF were characterized using Fourier-transform infrared spectroscopy, elemental analysis, and high-resolution 19 F NMR. MACF, chitosan, primary and secondary amine, octadecylsilane, graphitized carbon black, Z-Sep, Z-Sep+ , and EMR-Lipid were compared in terms of extraction efficiency. The best results were obtained when MACF was used. Matrix-matched calibration was employed for quantification. All the OPPs exhibited good linearity (r2 > 0.9969) with the concentration at their respective concentration ranges. The limits of detection were 1.5-3.0 µg/kg, and the limits of quantification were 5.0-10.0 µg/kg. The trueness of the 20 pesticides at four spiked levels ranged from 86.1 to 111.1%, and the relative standard deviation was less than 11.3%. The modified QuEChERS method using MACF as the adsorbent was sensitive, reliable, and cost-effective and could be used for the determination of 20 OPP residues in ginseng.

Evaluation of the automated micro-solid phase extraction clean-up system for the analysis of pesticide residues in cereals by gas chromatography-Orbitrap mass spectrometry.

Food analysis is a tremendously broad field that is constantly evolving. New methods have emerged to increase productivity, such as modern miniaturized and robotic analytical techniques. In this paper, a micro-solid-phase extraction system (µ-SPE) for clean-up was combined with a robotic autosampler to yield ready-to-analyze extracts. The system was evaluated for its applicability in routine laboratories. The new, automated, high-throughput µ-SPE clean-up method was applied to acetonitrile extracts and was developed for the analysis of pesticide residues in cereals by gas chromatography-Orbitrap mass spectrometry (GC-Orbitrap-MS). The µ-SPE clean-up efficiency was demonstrated in the removal of matrix-interfering components and in the recovery of pesticides. The sorbent bed mixture consisted of magnesium sulfate, primary-secondary amine, C18, and CarbonX, and effectively retained matrix components without loss of target analytes. Analysis of five types of cereals (barley, oat, rice, rye, and wheat) by GC-Orbitrap-MS showed that the method removed more than 70% of matrix components. The clean-up method was validated for 170 pesticides in rye, 159 pesticides in wheat, 142 pesticides in barley, 130 pesticides in oat, and 127 pesticides in rice. Spike recovery values were 70-120% for all pesticides and the repeatability, calculated as the relative standard deviation, was less than 20%. The limits of quantitation achieved were 0.005 mg kg-1 for almost all analytes, ensuring compliance with the maximum residue limits.