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BackgroundOrganophosphorus pesticides (OP) have been associated with various human health conditions. Animal experiments and in-vitro models suggested that OP may also affect the gut microbiota. We examined associations between ambient chronic exposure to OP and gut microbial changes in humans.MethodsWe recruited 190 participants from a community-based epidemiologic study of Parkinson's disease living in a region known for heavy agricultural pesticide use in California. Of these, 61% of participants had Parkinson's disease and their mean age was 72 years. Microbiome and predicted metagenome data were generated by 16S rRNA gene sequencing of fecal samples. Ambient long-term OP exposures were assessed using pesticide application records combined with residential addresses in a geographic information system. We examined gut microbiome differences due to OP exposures, specifically differences in microbial diversity based on the Shannon index and Bray-Curtis dissimilarities, and differential taxa abundance and predicted Metacyc pathway expression relying on regression models and adjusting for potential confounders.ResultsOP exposure was not associated with alpha or beta diversity of the gut microbiome. However, the predicted metagenome was sparser and less evenly expressed among those highly exposed to OP (p = 0.04). Additionally, we found that the abundance of two bacterial families, 22 genera, and the predicted expression of 34 Metacyc pathways were associated with long-term OP exposure. These pathways included perturbed processes related to cellular respiration, increased biosynthesis and degradation of compounds related to bacterial wall structure, increased biosynthesis of RNA/DNA precursors, and decreased synthesis of Vitamin B1 and B6.ConclusionIn support of previous animal studies and in-vitro findings, our results suggest that ambient chronic OP pesticide exposure alters gut microbiome composition and its predicted metabolism in humans.

A straightforward and fast magnetic dispersive solid-phase microextraction method (MDSPME) as a sample preparation procedure coupled with gas chromatography/mass spectroscopy (GC/MS) was developed to measure three organophosphorus pesticides (OPPs), including ethion, diazinon, and chlorpyrifos, from fruit and cereal samples. Magnetic Fe3O4@ reduced graphene oxide nanocomposites as an excellent sorbent were synthesised based on several steps such as graphite oxide preparation, graphite oxide exfoliation, graphene oxide reduction, and chemical co-precipitation of magnetic Fe3O4 methods. Nine factors affected in the MDSPME procedure were thoroughly optimised using the design of experiment approach. The Plackett-Burman design and central composite design were utilised for screening the significant factors and for optimising the factors, respectively. The calibration curves of ethion, diazinon, and chlorpyrifos were linear in the ranges of 0.008–4.5, 0.01–4.0, and 0.01–4.5 ng ml−1 with R-squared of 0.9953, 0.9923, and 0.9981, respectively. The proposed method has high preconcentration factors (PF ≥ 220), low sample solution consumption (5.0 ml), and fast extraction time (5.0 min) for the OPPs determination. Analysis of real samples, including rice and cucumber samples, was shown that the proposed procedure is the suitable sample preparation and determination method for the measurement of OPPs with a recovery percentage in the range of 91.3%-102.2% and RSDs lower than 7.2%. The method has great advantages including low desorption solvent consumption, simple operation, and suitable RSDs for the OPPs determination in the fruit and cereal samples with complex matrices. [ABSTRACT FROM AUTHOR]

Synthesis of highly fluorescent carbon dots from an agro crop through facile one-pot microwave method has been reported. Bilimbi fruit derived carbon dots named as BCDs, exhibited excellent photoluminescent properties and stability. Fluorescence of the system selectively quenched on interaction with Cu(II), due to the complex formation between amine, hydroxyl and carboxyl groups in the surface of the BCDs with Cu(II). The non-fluorescent complex displayed a selective and sensitive turn-on fluorescence behaviour on adding organophosphorus pesticide quinalphos. And hence, the prepared system is used for dual sensing purposes with nanomolar level of detection limits. The limit of detection of Cu(II) and quinalphos was estimated as 115 nM and 510 nM, respectively. The entire detection process was visible under UV light of 365 nm. Moreover, the BCDs@Cu(II) nanoprobe was effectively applied as fluorescence sensor of quinalphos in real samples of rice and tea where its presence is frequently reported, with good level of recovery percentages. [ABSTRACT FROM AUTHOR]

Effective recycling of organic residues contributes to solving energy crisis and resource recycling. In Egypt, sugarcane is considered one of the most produced agricultural product, which in terms leads to the production of a vast amount of its by-products. In this work, for the first time, untreated sugarcane bagasse (SCB) was utilised as a sorbent in the solid-phase extraction (SPE) of selected pesticides including chlorfenvinphos, chlorpyrifos, diazinon, ethion, profenofos (organophosphorus compounds) and cyprodinil (anilinopyrimidine) from water. Optimal parameters influencing the recovery of the studied pesticides including eluting solvent (type, volume and pH), amount of sorbent and water pH were adjusted. Method performance criteria using SCB cartridges were compared with that of commercial SPE cartridges, indicating SCB as an effective and green chemistry alternative. The final SPE procedure can be briefly described as follows: the SCB (500 mg) SPE cartridge was conditioned with 5 mL methanol followed by 5 mL distilled water. Then, 500 mL water sample (DIW) was loaded on the SCB SPE cartridge. Afterwards, the cartridge was dried using nitrogen for 15 min. Then, 4 mL acetonitrile containing 5% formic acid was used as the eluting solvent to be analysed using LC-MS/MS. The method was validated in accordance with (SANTE/2020/12830 and Eurachem Second Edition 2014). Rapid adsorption and desorption performance for SCB was confirmed by using adsorption kinetic and isotherm studies. Finally, five environmental water samples were analysed using the developed method, only one sample had positive result (profenofos 0.01 µg/L), which is below the accepted limits. [ABSTRACT FROM AUTHOR]

Pesticides are applied widely to increase agricultural output and quality, however, this practice results in residual issues that not only harm the environment but also put people and animals' lives and health at risk. As a result, it is critical to find pesticide residues in a variety of sources, including crops, water supplies, and soil. Aptamers are more flexible in their synthesis and modification, have a high level of specificity, are inexpensive, and have good stability compared to conventional detection methods. They have therefore attracted a lot of interest in the industry. This study reviews the most recent aptasensor advancements in the detection of pesticide residues. Firstly, aptamers specifically binding to many pesticides are summarized. Secondly, the combination of aptasensors with colorimetric, fluorescent, surface enhanced Raman spectroscopy (SERS), resonance Light Scattering (RLS), chemiluminescence (CL), electrochemical, and electrochemiluminescence (ECL) technologies are systematically introduced, and their advantages and disadvantages are expounded. Importantly, the aptasensors for the detection of various pesticides (organochlorine, organophosphorus, neonicotinoids, carbamates, and pyrethroids) that have been developed so far are systematically analyzed and discussed. Finally, the furture prospects and challenges of the aptasensors are highlighted. It is expected to offer suggestions for the later creation of novel, highly effective and sensitive aptasensors for the detection of pesticide residues. [ABSTRACT FROM AUTHOR]

Organophosphorus pesticides are commonly employed in agricultural fields due to their potent insecticidal properties and short environmental persistence. However, organophosphorus pesticides enter the human body through the food chain, surface, and groundwater, leading to irreversible damage to the nervous system. Therefore, monitoring the presence of organophosphorus pesticides in food is necessary to ensure human safety. Herein, an ultra‐sensitive electrochemical biosensor has been prepared by using graphitic carbon nitride decorated molybdenum sulfide (g‐C3N4@MoS2) as a catalyst for the detection of organophosphorus pesticides, trichlorfon. The synergistic effect of g‐C3N4@MoS2 boosts the electron transfer across the electrode surface, further contributing to the immobilization of acetylcholinesterase (AChE) enzyme using glutaraldehyde as a crosslinking agent. At optimum conditions, the developed biosensor (AChE/g‐C3N4@MoS2/ITO) demonstrated a broad linear range (5–100 nM) with a low detection limit (LOD) of 2.1 nM obtained using the equation 3σ/S where σ is the standard deviation and S is the sensitivity of the bioelectrode. In addition, the AChE/g‐C3N4@MoS2/ITO biosensor exhibited good stability and reproducibility, with satisfactory results for real sample analysis of trichlorfon detection. [ABSTRACT FROM AUTHOR]

This work investigates the validation of the SW-ASV method for the determination of malathion organophosphorus pesticide based on an electrochemically modified (CPE) carbon paste electrode with copper metal. The surface of the modified CPE was constructed by electrodepositing the copper layer at the accumulation step in 1-mM CuSO4.5H2O, PBS at pH 6.6, E accumulation: − 0.8 V, and Taccumulation 240 s. The determining step was performed by adding different concentrations of malathion pesticide and applying the potential toward more positive potential at (− 0.8–+ 1.4 V) to enhance the oxidation of Cu0 metal. It was noticed that the malathion concentration gradient enhances the oxidation peak current of copper at + 0.03 V gradually. SW-ASV method validation was performed at a linearity range confined in (1–10 µM). An analytical curve was constructed and R2 was equal to 0.99995 with good fitted linear relationship. LOD and LOQ were calculated to be 0.0247 and 0.08236 µM, respectively. ANOVA for two sets of measurements using the standard gas chromatographic method and the suggested SW-ASV method was demonstrated via the calculations of F-value and t-value. F and t-values were calculated to be 1.698 and 0.289, respectively, which did not exceed the tabulated F and t-values resulting in the great similarity of results and ensuring the reliability of the suggested test method. This valid SW-ASV method was used to perform the routine analysis of the 95% technical grade and the pesticide formulation 57% emulsion concentrate of the malathion. Valid results were achieved with satisfactory limits of accuracy and precision. [ABSTRACT FROM AUTHOR]

Glyphosate (GH) wastewater potentially poses hazards to human health and the aquatic environment, due to its persistence and toxicity. A highly superhydrophilic and stable graphite felt (GF)/polydopamine (PDA)/titanium dioxide nanotubes (TiO2-NT)/SnO2/Ru anode was fabricated and characterized for the degradation of glyphosate wastewater. Compared to control anodes, the GF/PDA/TiO2-NT/SnO2/Ru anode exhibited the highest removal efficiency (near to 100%) and a yield of phosphate ions of 76.51%, with the lowest energy consumption (0.088 Wh/L) for degrading 0.59 mM glyphosate (GH) at 7 mA/cm2 in 30 min. The exceptional activity of the anode may be attributed to the co-activation of lattice oxygen in TiO2-NT and SnO2 by coupled Ru, resulting in a significant amount of •O2− and oxygen vacancies as active sites for glyphosate degradation. After electrolysis, small molecular acids and inorganic ions were obtained, with hydroxylation and dephosphorization as the main degradation pathways. Eight cycles of experiments confirmed that Ru doping prominently enhanced the stability of the GF/PDA/TiO2-NT/SnO2/Ru anode due to its high oxygenophilicity and electron-rich ability, which promoted the generation and utilization efficiency of active free radicals and defects-associated oxygen. Therefore, this study introduces an effective strategy for efficiently co-activating lattice oxygen in SnO2 and TiO2-NT on graphite felt to eliminate persistent organophosphorus pesticides. [ABSTRACT FROM AUTHOR]

With growing concerns regarding environmental pollution and the need for sustainable waste management practices, this study investigates the potential of utilizing spent coffee grounds (SCG) as a precursor for producing functional carbon materials aimed at organophosphorus pesticide remediation under environmentally relevant conditions. Carbonization of SCG is followed by various activation methods, including treatment with potassium hydroxide, phosphoric acid, and carbon dioxide, individually or in combination. The resulting biochars are systematically analyzed for their adsorption performance towards malathion and chlorpyrifos. Screening tests revealed a selective adsorption preference towards aromatic chlorpyrifos over aliphatic malathion. Activation processes significantly influence adsorption kinetics and efficiency, with physical activation showing notable adsorption rates and capacity enhancements. Moreover, the SCG-derived biochars exhibit a pronounced dependency on adsorption temperature. Adsorption, regeneration, and reuse of the most promising material are tested in a real, spiked tap water sample, proving that the presence of ions in tap water did not affect the adsorption and that the material has the potential to be reused more than ten times. This work proposes a straightforward approach for recycling SCG by converting it into functional carbon materials, underscoring the importance of selecting the appropriate activation processes and conditions for practical applications in pesticide remediation. [ABSTRACT FROM AUTHOR]

Copyright of Food & Fermentation Industries is the property of Food & Fermentation Industries and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Methidathion (MTDT), a common organophosphorus pesticide with high insecticidal activity, is widely used for pest control. However, the misuse of MTDT leads to widespread residues and endangers human health. Therefore, it is crucial to develop a simple and highly sensitive method for the detection of MTDT residues. Herein, ZIF-90/MnO2/g-C3N4/Fe3O4 composite particles were synthesized: The MnO2 nanosheets could absorb the energy of the excited g-C3N4 to quench the ECL of g-C3N4 while ZIF-90 acted as a mimetic enzyme to catalyze the formation of thiocholine from MTDT. The thiocholine caused the reduction of MnO2 to Mn2+, restoring the ECL signal of g-C3N4. Combined with molecular imprinting technique, an electrochemiluminescence sensor was constructed for the determination of MTDT. The determination range was 1.00 × 10–9 ~ 7.00 × 10–7 g/L, and the detection limit was 6.58 × 10–10 g/L. Structurally similar organophosphorus pesticides showed no cross-reactivity. The method has high sensitivity and specificity, and has been successfully applied to the determination of MTDT residue in fruits with recoveries in the range 93.75% ~ 102.37%. [ABSTRACT FROM AUTHOR]

The extensive usage of organophosphate pesticides (OPs) has posed severe harm to human health and environmental system, but achieving highly effective and on-site detection is still a great challenge. In this work, a novel nanozyme Nb2CTx MXene/bimetallic PdPt (Nb2CTx@PdPt) was synthesized firstly through a simple self-reduction method, and the results show that the as-prepared Nb2CTx@PdPt nanozyme exhibits outstanding peroxidase-like activity. Interestingly, the nanozyme activity of Nb2CTx@PdPt is restrained remarkably in the presence of acetylcholine chloride and acetylcholinesterase while it can be restored through the addition of OPs (selecting glyphosate as a model). Based on this phenomenon, a sensitive colorimetric assay coupled with hydrogel and smartphone for OPs was then constructed. After optimizing various conditions, the designed sensing platform can achieve stable, rapid, and sensitive on-site detection for OPs, showing superior sensing performances: a wide linearity of 1.0 ng mL−1–1.0 µg mL−1 and low detection limit of 0.419 ng mL−1. [ABSTRACT FROM AUTHOR]

DNA walker nanomachines are in fast development for biosensing, medical diagnostics, and food safety monitoring. For practical application, the issues of slow dynamics and low operational efficiency hinder its widespread application. Inspired by the high efficiency of agricultural cooperative machinery, a unique cleaving‐rolling‐assembly integrated nanodevice (CRAIN) is constructed for the high‐performance detection of various biomolecules. In the design, DNA nanotubes are introduced as building loaders to engineer polyoriented walking DNA nanorollers with blocked DNAzyme‐based walking strands and thus to increase the reaction direction and local concentration. Through target‐specific recognition, the activated nanorollers can autonomously and progressively cleave and roll along directional hairpin tracks on a gold substrate, significantly accelerating the reaction rate. Moreover, using nucleic acid‐encoded urchin‐shaped multispike gold‐silver composite nanospheres (nMGSs) as SERS‐enhanced probes, the engineered assembly of nMGSs probes induced by the cleaving‐rolling process promotes the formation of high‐density hotspot domains, further improving the detection sensitivity. With rational design, the CRAIN system can be extended to perform highly sensitive analyses of various analytes, such as microRNA‐21, butyrylcholinesterase activity and organophosphorus pesticides. This integrated assembly strategy can provide new perspectives for clinical diagnosis, biomedical engineering, and environmental science. [ABSTRACT FROM AUTHOR]

The intensive application of organophosphorus pesticides (OPs) and their acute toxicity have raised significant threats to human health. Herein, an electrochemiluminescence (ECL) nanomaterial was synthesized by successive modification of the Zn–N structure and Prussian blue (PB) nanoparticles on cerium-(III) tetrakis-(4-carboxyphenyl)-porphine (CeTCPP). Because of the combination of CeTCPP (luminophore) and the Zn–N structure (coreaction accelerator) in one nanostructure, Zn-CeTCPP exhibited a high ECL response based on the self-enhancement strategy. The ECL signal was remarkably quenched in turn due to the resonance energy transfer (RET) from Zn-CeTCPP to PB. However, PB was disassembled in the presence of acetylcholinesterase and acetylthiocholine since the produced acetic acid and thiocholine destroyed PB and reduced PB to Prussian white, respectively. Therefore, the recovered ECL signal was employed to sensitively detect malathion with a wide linear range of 1.0 × 10–13–1.0 × 10–7 g/mL and a low limit of detection of 13 fg/mL, endowing the present ECL-RET sensor with excellent prospects for practical application based on the self-enhancement and acceptor disassembly strategies. [ABSTRACT FROM AUTHOR]

This article explores the ionization characteristics of 19 amino acids using positive-ion Helium-Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry (He-DART-MS). The study reveals that multiple hydrogenation radical adducts of amino acids were observed during He-DART-MS analysis, with heterocyclic amino acids being more likely to produce these adducts. Aromatic amino acids, on the other hand, were less likely to exhibit this phenomenon. The findings provide valuable insights for the analysis of related compounds using He-DART-MS. The study received support from the Science and Technology Development Planning Project of Jilin Province and the Project for Outstanding Young Scientific and Technological Talents of Changchun University of Chinese Medicine. [Extracted from the article]

Hydrophilicity‐hydrophobicity modulation of active sites provides a promising strategy for enhancing catalytic performance. Current researches focus on the influence of substrate molecules, however, the role of H2O molecules is often overlooked in nanozyme‐catalyzed reactions. Herein, bioinspired Pt@ZIF‐R (R = ‐90, ‐8, ‐8@TMS, where TMS is tetraethoxysilane) nanozymes are designed as model catalysts, with Pt nanoparticles as active centers and metal organic‐framework nanocavities as hydrophilic‐hydrophobic binding pockets, revealing the critical role of H2O in the peroxidase‐like catalytic process of H2O2 decomposition. A positive correlation between catalytic activity and hydrophobicity is observed, and strong hydrophobic Pt@ZIF‐8@TMS nanozyme exhibits the best catalytic performance. Theoretical calculations indicate that as hydrophobicity increases, solvent H2O reduces the competitive adsorption with H2O2 and decreases the energy barrier of the rate‐determining step (2*O→*O2) simultaneously. In addition, the desorption of the product H2O is thermodynamically favorable with increasing hydrophobicity. Importantly, Pt@ZIF‐8@TMS nanozyme is successfully used to develop a colorimetric biosensor for the detection of organophosphorus pesticides, with a detection limit as low as 0.7 ng mL−1, which is superior to numerous existing methods. This work provides fundamental insights into the function of hydrophobicity in boosting catalytic activity, which may offer guidance for the development of efficient nanozymes. [ABSTRACT FROM AUTHOR]

Background: WHO has estimated that around 300 million individuals are subjected to pesticide poisoning annually, leading to roughly 200,000 deaths each year in developing nations. C reactive protein is well known as an inflammatory indicator that is elevated in injury, trauma, infection, cancer and autoimmune diseases. However very little is known about the role of CRP on acute poisoning. Objective of The Study: 1. To assess the severity and prognosis of acute organophosphorus poisoning by C-Reactive Protein. Materials and Methods: It is a prospective, observational study conducted from August 2022 to July 2024 at GIMS, Kalaburagi. Sample size included 100 individuals who were hospitalized due to organophosphorus poisoning to GIMS hospital during the study period. Patients were reviewed daily until discharge or death. C-Reactive Protein (CRP) levels were measured at admission, 72 hours post-admission and on day 7 or day of discharge/death. Results: The mean CRP levels of the expired patients were significantly higher than those of the live patients at admission, at 72 hours and at discharge (p<0.001). Conclusion: In conclusion, the present study revealed that changes in CRP was associated with the prediction of AOPP prognosis. Patients with severe acute organophosphorus pesticide poisoning show elevated levels of Creactive protein, which play a significant role in predicting the severity and prognosis of the condition. [ABSTRACT FROM AUTHOR]

Chlorpyrifos, one of the most frequent organophosphorus pesticides, has been linked to major health problems and widespread environmental degradation. It is imperative to remove this herbicide from its point source of contamination since the risk of their off-site migration poses a health concern to non-target organisms. The objective of the present study was to investigate the biodegradation of chlorpyrifos 20% emulsifiable concentration (EC) utilizing a consortium of bacteria that had previously been isolated from a pesticide-contaminated site and are chlorpyrifos tolerant (S27I and S28I). Free cells and immobilized cells with chlorpyrifos as the only carbon source were used to analyze the biodegradation. Charcoal–alginate and kaolin–alginate were the immobilization matrices employed in the investigation. By using gas chromatography-mass spectrophotometer analysis, the degradation of chlorpyrifos was investigated. When compared to free cells, immobilized bacterial isolates showed the greatest amount of biodegradation in the investigation. Consortium (C1) among the isolates degraded chlorpyrifos most quickly compared to S27I and S28I. The study also examined the toxicity of chlorpyrifos at doses of 10, 25, 50, 75, and 100 ppm on the green gram seeds' morphological parameters. Increased chlorpyrifos concentrations resulted in appreciable variations in the germination percentage, shoot length, and root length. The green gram germination study was used to evaluate the detoxification of chlorpyrifos following its breakdown. [ABSTRACT FROM AUTHOR]

Organophosphate (OP) poisoning, both accidental and with suicidal intent, is a global medical challenge. While the primary toxicity of these pesticides is based on the inhibition of acetylcholinesterase (AChE), case reports describe patients developing OP-mediated renal insufficiency. We set out to investigate possible pathomechanisms utilizing rat precision-cut kidney slices (PCKS). Depending on the method of investigation, PCKS were observed for a maximum of 10 days. PCKS exposed to OP compounds (malaoxon, malathion, paraoxon, parathion) showed a dose-dependent loss of viability and a reduction of total protein content over the course of 10 days. A concentration of 500 µM OP showed the most differences between OP compounds. After two days of incubation parathion showed a significantly lower level of viability than malathion. The respective effects of paraoxon and malaoxon were not significantly different from the control. However, effects of OP were only observed in concentrations exceeding those that were needed to achieve significant AChE inhibition in rat kidney tissue. In addition, we observed histological changes, without inducing LDH leakage. Overall, results suggest that OP exert effects in kidney tissue, that exceed those expected from the sole inhibition of AChE and vary between compounds. Without signs of necrosis, findings call for studies that address other possible pathomechanisms, including inflammatory response, oxidative stress or activation of apoptosis to further understand the nephrotoxicity of OP compounds. Monitoring oxon concentration over time, we demonstrated reduced enzyme-inhibiting properties in the presence of PCKS, suggesting interactions between OP compound and kidney tissue. [ABSTRACT FROM AUTHOR]

The use of agricultural pesticides in modern agriculture has permitted enormous and reliable production. The organophosphorus pesticide fenitrothion (FT) is widely used in agricultural regions and has been related to detrimental effects on human health. We constructed an electrochemical sensor that detects fenitrothion (FT) using one-dimensional (1D) Pr2(WO4)3 nanorods (PWO) incorporated reduced graphene oxide (RGO) electrocatalyst that was synthesized hydrothermally. The PWO nanorods are finely embedded on the RGO nanosheet, according to powder XRD, FESEM, EDS, HRTEM, XPS, and micro-Raman studies. The PWO/RGO electrochemical behavior towards FT was studied by the different electrochemical characterization approaches [CV, DPV, AMP(i–t)]. Our proposed PWO/RGO sensor exhibited a linear range of 0.01–313 µM and an LOD of 0.0054 µM in AMP(i–t). The estimation of FT in different water samples proves the usefulness of the PWO/RGO sensor. [ABSTRACT FROM AUTHOR]

A new method is presented for the simultaneous determination of 13 multiclass pesticides along with glyphosate. The multiclass pesticides were extracted by creating a soil slurry with 2% ethanol in water (v/v), and then, applying direct-immersion solid-phase microextraction (DI-SPME) with a new type of semi-disposable SPME fiber configuration called LC-Tips. The fibers were then retroextracted to ethanol, and aqueous ammonia was added to the slurry to extract glyphosate. Derivatization of the glyphosate extract was accomplished with a mixture of trifluoroacetic anhydride and trifluoroethanol, after which the reaction mixture was dried and resuspended with the SPME ethanol extract. To this, a mixture of analyte protectants was added, and it was analyzed by GC-MS/MS in multiple-reaction-monitoring mode. All analytes showed a coefficient of determination greater than 0.95 in the 0.1–100 µg/kg calibrated range, and the limits of detection were between 0.1 and 1 µg/kg, except for glyphosate, which was 0.01 µg/kg. The method shows relatively high replicate relative standard deviation (as much as 37% for five extractions at 20 µg/kg), but the isotopically labeled internal standard was effective at mitigating this effect for some analytes. [ABSTRACT FROM AUTHOR]

Copyright of Shipin Kexue/ Food Science is the property of Food Science Editorial Department and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The possibility of the elution of hydrophilic organophosphorus substances using a concentration gradient of formic acid in an aqueous mobile phase on a Hypercarb porous graphitized carbon sorbent is studied. The analytes are detected on a monoquadrupole mass spectrometer. The retention of analytes is studied by varying the composition of the mobile phase before injection of the sample solution. It is shown that the effect of the stepwise gradient elution on the retention of analytes is primarily due to the state of the sorbent surface rather than the elution ability of the phases. The displacement "quasi-ion exchange" mechanism of analyte retention seems to be most probable. [ABSTRACT FROM AUTHOR]

Concerns regarding human health and food safety have generated interest in developing simple, accurate, and cost-effective strategies for evaluating organophosphorus pesticide (OP) residues. In this study, nitrogen-doped carbon dots (N-CDs) were synthesized from a common low-cost precursor via a simple pyrolysis process. The fluorescence of the N-CDs can be suppressed by p-nitrophenol, which is the hydrolysis product of the p-nitrophenyl phosphate salt catalyzed by alkaline phosphatase (ALP). A fluorescent turn-on assay for the inhibitory effect of glyphosate was developed with a low detection limit and wide linear range. Moreover, the feasibility of visualizing OPs in vegetables was demonstrated by the fluorescence imaging of glyphosate on cabbage leaves. This research not only offers a facile method for the synthesis of highly fluorescent CDs but also inspires the development of effective multi-mode sensing platforms that include fluorescent testing and imaging for monitoring pesticide residues. [ABSTRACT FROM AUTHOR]

After high-temperature etching of metal-free porous N -doped carbon with NaCl, the doped Cl atoms significantly enhance the peroxidase-like activity of the nanozyme. [Display omitted] Metal-free carbon-based nanozymes often exhibit superior chemical stability and detection reliability compared to their metal-doped counterparts. However, their catalytic activity remains an area ripe for further enhancement. Herein, we successfully prepared a chlorine (Cl)-modified, metal-free, and porous N -doped carbon nanozyme (Cl x -pNC) via NaCl molten etching. The incorporation of Cl induced an increase in the intrinsic defects of sp3-hybridized carbon within Cl x -pNC and optimized the electronic structure of the N -connected carbon atoms. Remarkably, the peroxidase (POD)-like activity of Cl x -pNC was enhanced twelvefold compared to porous N -doped carbon (pNC). Theoretical simulations highlighted that the introduction of Cl not only promoted H 2 O 2 adsorption but also lowered the energy barrier for its decomposition, facilitating the generation of active intermediates and thus boosting POD-like activity. Based on the POD mimic activity of Cl x -pNC, we developed a colorimetric platform for OPs detection utilizing a cascade amplification strategy. This work provides insights into the rational design of carbon-based nanozymes and the development of nanozyme-based colorimetric biosensors. [ABSTRACT FROM AUTHOR]

[Display omitted] • The Al 6 Si 2 O 13 /WO 2.72 nanocomposites exhibits excellent photocatalytic activity and stability in degrading triazophos pesticides, reducing the rate from 100.0% to 13.7% in 140.0 min. • The S-scheme heterojunction significantly enhances photocatalytic performance by improving charge separation and minimizing recombination. • Abundant oxygen vacancies combined with the S-scheme heterojunction accelerate charge separation, further enhancing photocatalytic degradation activity. The environmental contamination caused by organophosphorus pesticides (for example, triazophos) is an escalating concern. To mitigate this issue, this study introduces a novel Al 6 Si 2 O 13 /WO 2.72 (ASO/WO) nanocomposite photocatalyst, which markedly enhances the photocatalytic degradation of triazophos. The optimized nanocomposite material with a 60.0 % ASO loading (60-ASO/WO) achieves a degradation rate of 86.3 % for triazophos within 140.0 min, marginally exceeding 60-ASO/WO 3 (72.6 %) and significantly outperforming individual ASO (65.0 %), WO (59.5 %), and WO 3 (56.2 %). This catalyst retains 88.9 % of its activity after five cycles, showcasing exceptional efficiency and stability. Additionally, its electrochemical surface area (ECSA, 310.0 cm2), total organic carbon (TOC, removal rate of 73.7 %), photocurrent, and electrochemical impedance are all optimal. X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and theoretical calculations elucidate the critical role of oxygen vacancies and the S-scheme heterojunction in augmenting charge separation and photocatalytic performance, corroborating the synergistic effect of oxygen defects and the S-scheme. While individual factors can enhance photocatalytic activity, their combination results in a more pronounced effect. Liquid chromatography-mass spectrometry (LCMS) identifies the principal degradation intermediates, including 1-phenyl-3-hydroxy-1, 2, 4-triazole, diethyl thiophosphate, and 3, 5, 6-trichloro-2-pyridinol, underscoring the material's potential in environmental remediation. [ABSTRACT FROM AUTHOR]

A sensitive platform was constructed for on-site detection of chlorpyrifos by immobilizing a core–shell structured NaYbF 4 @NaYF 4 : Yb3+, Tm3+ UCNPs/MnO 2 composite in calcium alginate hydrogel kit. Specifically, the designed UCNPs fluorescent probe (NaYbF 4 @NaYF 4 : Yb3+, Tm3+) has the blue-violet emission. After mixing with MnO 2 nanoflakes, the blue-violet upconversion (UC) emission is quenched. Thiocholine (TCh), formed through acetylcholinesterase (AChE)-mediated catalysis, reduces MnO 2 nanoflakes to Mn2+ ions, thereby restoring the system's fluorescence. The introduction of chlorpyrifos inhibits AChE activity, accompanied by the quenching of the fluorescence signal. Based on the blue-violet UC emission signal response to chlorpyrifos, fluorescent photos were taken by smartphones. Utilizing a Python-assisted analysis platform, a "one-run" operation simultaneously captures image grayscale values, gray images, and differentiated pseudo-color images related to pesticide concentrations, enabling real-time and rapid quantitative analysis of pesticides. [Display omitted] On-site quantitative analysis of pesticide residues is crucial for monitoring environmental quality and ensuring food safety. Herein, we have developed a reliable hydrogel portable kit using NaYbF 4 @NaYF 4 : Yb, Tm upconversion nanoparticles (UCNPs) combined with MnO 2 nanoflakes. This portable kit is integrated with a smartphone reader and Python-assisted analysis platform to enable sample-to-result analysis for chlorpyrifos. The novel UCNPs maximizes energy donation to MnO 2 acceptor by employing 100 % of activator Yb3+ in the nucleus for NIR excitation energy collection and confining emitter Tm3+ to the surface layer to shorten energy transfer distance. Under NIR excitation, efficient quenching of upconversion blue-violet emission by MnO 2 nanoflakes occurs, and the quenched emission is recovered with acetylcholinesterase-mediated reactions. This process allows for the determination of chlorpyrifos by inhibiting enzymatic activity. The UCNPs/MnO 2 were embedded to fabricate a hydrogel portable kit, the blue-violet emission images captured by smartphone were converted into corresponding gray values by Python-assisted superiority chart algorithm which achieves a real-time rapid quantitative analysis of chlorpyrifos with a detection limit of 0.17 ng mL−1. At the same time, pseudo-color images were also added by Python in "one run" to distinguish images clearly. This sensor detection with Python-assisted analysis platform provides a new perspective on pesticide monitoring and broadens the application prospects in bioanalysis. [ABSTRACT FROM AUTHOR]

Organophosphorus pesticides (OPPs) are a group of pesticides that are most widely used in the agricultural sector, and farmers are exposed to these chemicals more than other members of society. In this work, an environmentally friendly, simple, and safe ultrasound-assisted dispersive liquid-liquid microextraction (USA–DLLME) method using alcohol-based hydrophobic deep eutectic solvents (HDESs) followed by gas chromatography-mass spectroscopy (GC–MS) was developed for the extraction and determination of OPPs in the blood of farmers studied in Ravansar cohort. DESs synthesized from thymol as hydrogen bond donor (HBD) and aliphatic alcohols as hydrogen bond acceptor (HBA) have been used as extractants. Under optimal experimental conditions, the reproducibility of the method based on 7 replicate measurements of 10 µg L−1 of OPPs in blood samples was in the range of 1.4–3.8%. The method showed a linearity in the range of 0.01–150 µg L−1. The limits of detection and limits of quantification were between 0.003 and 0.02 µg L−1 and 0.01–0.05 µg L−1, respectively. The matrix effect and accuracy of the method were confirmed by spiking different amounts of OPPs in real blood samples and obtaining relative recoveries in the range of 91–112%. The results showed that the concentration of OPPs in the case group was significantly higher than in the control group, which is because the case group was exposed to OPPs during the spraying of agricultural products. [ABSTRACT FROM AUTHOR]

A new nanocarrier was developed for the delivery of an antidote for poisoning with organophosphorus compounds. The nanocarrier acts as an artificial esterase, hydrolyzing acetylcholine and releasing the antidote (atropine) when acetylcholine level is high. The nanocarrier was made using histidine-containing resorcinarene as a building block. Histidine-resorcinarene was preorganized in a microemulsion media and then polymerized with phenylboronic acid, which acts as a linker between the resorcinarene molecules. Antidote (atropine) was incorporated into the nanocarrier with an encapsulation efficiency of 52.2%. At a neutral pH of 7.4, the nanocarrier hydrolyzes acetylcholine to choline and acetic acid. The acid triggers dissociation of the boronate bonds to dissociate, resulting in nanocarrier degradation and the release of 64.4% of the antidote. Transmission electron microscopy (TEM), dynamic and static light scattering (DLS and SLS, respectively), and IR spectroscopy were utilized to characterize the structure of the nanocarriers. Cyclic voltammetry and NMR spectroscopy were employed to evaluate its ability to hydrolyze acetylcholine. Through fluorescence and NMR spectroscopy, it was demonstrated that the nanocarrier could release substrates (fluorescein and atropine) in in response to the presence of acetylcholine. [ABSTRACT FROM AUTHOR]

The unreasonable use of agrochemicals and various human activities in the environment of Al‐Sin Lake basin may cause pollution to water, especially with widely used organophosphate pesticides, which have an effect on the human nervous system. This research sought to determine concentrations of dichlorvos of the synthetic organophosphate pesticide in the waters of the environment surrounding Al‐Sin Lake in the Syrian coastal area. A questionnaire form was dispensed to the local residents in the region, to determine the status of the studied area. Ground and surface water samples were collected from several locations surrounding the Lake. The first site is surrounded by greenhouses and a citrus orchard. The second is the Surit spring. The third site includes greenhouses. The fourth site represents surface water (Lake Surit). The study lasted for seven consecutive months from December until June 2020–2021, samples were taken once a month. Various parameters (pH, EC, TDS, and PO4−3) were measured. Dichlorvos was extracted from the samples using solvents (hexane‐acetone) to be ready for analysis using high‐performance liquid chromatography. The results showed the presence of dichlorvos residues in the studied water samples, with average concentrations ranging between 0.2 and 1.3 µg.L−1, which were higher than the recommended value for individual pesticide in water (0.1 µg.L−1) as recommended by the European Union. Observations of dichlorvos concentration indicated some increase at lower pH. Consequently, contamination of ground and surface waters with dichlorvos was observed in the studied sites, because of its frequent use and its high solubility in water. This unregulated use of dichlorvos can pose a matter of public health concern. [ABSTRACT FROM AUTHOR]

Chiral pesticides account for about 40% of the total pesticides. In the process of using pesticides, it will inevitably flow into the surface water and even penetrate into the groundwater through surface runoff and other means, as a consequence, it affects the water environment. Although the enantiomers of chiral pesticides have the same physical and chemical properties, their distribution, ratio, metabolism, toxicity, etc. in the organism are often different, and sometimes even show completely opposite biological activities. In this article, the selective fate of different types of chiral pesticides such as organochlorine, organophosphorus, triazole, pyrethroid and other chiral pesticides in natural water bodies and sediments, acute toxicity to aquatic organisms, chronic toxicity and other aspects are summarized to further reflect the risks between the enantiomers of chiral pesticides to non-target organisms in the water environment. In this review, we hope to further explore its harm to human society through the study of the toxicity of chiral pesticide enantiomers, so as to provide data support and theoretical basis for the development and production of biochemical pesticides. [ABSTRACT FROM AUTHOR]

Dimethoate (DMT) is one of the most harmful and commonly used organophosphate pesticides in agricultural lands to control different groups of parasitic insects. However, this pesticide is considered a dangerous pollutant for aquatic organisms following its infiltration in coastal ecosystems through leaching. Yet, our investigation aimed to gain new insights into the toxicity mechanism of DMT in the muscles of the green crab Carcinus aestuarii, regarding oxidative stress, neurotransmission impairment, histological aspects, and changes in lipid composition, assessed for the first time on the green crab's muscle. Specimens of C. aestuarii were exposed to 50, 100, and 200 µg DMT L−1 for 24 h. Compared to the negative control group, the higher the DMT concentration, the lower the saturated fatty acids (SFA), and the higher the monounsaturated fatty acids (MUFA). The significant increase in polyunsaturated fatty acid n-6 (PUFA n-6) was related to the high release, mainly, of linoleic acid (LA, C18: 2n6) and arachidonic acid (ARA, C20: 4n6) levels. Biochemical biomarkers showed that DMT exposure promoted oxidative stress, highlighted by increased levels of hydrogen peroxide (H2O2), malondialdehyde (MDA), advanced oxidation protein product levels (AOPP), and protein carbonyl (PCO). Furthermore, the antioxidant defense system was activated, as demonstrated by the significant changes in the enzymatic activity of superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), and reduced glutathione (GSH) levels associated with an adaptation process of C. aestuarii to cope with the DMT exposure. This pesticide significantly impairs the neurotransmission process, as evidenced by the inhibition of acetylcholinesterase (AChE) activity. Finally, several histopathological changes were revealed in DMT-treated crabs, including vacuolation, and muscle bundle loss. This research offered new insights into the toxic mechanism of DMT, pointing to the usefulness of fatty acid (FA) composition as a sensitive biomarker in littoral crabs. [ABSTRACT FROM AUTHOR]

The muscle tissues of Channa punctatus and Anabas testudineus collected from the Loktak Lake (a Ramsar site) and its three major feeder rivers in Manipur, Northeastern India, were analyzed using high-performance liquid chromatography for the presence of residues of organophosphorus, carbamate, and synthetic pyrethroid pesticides. Pesticide residues of all the three typeswere detected in the fish tissues. Pesticide residues in Channa punctatus ranged from 0.002-0.043 μg g-1, and from 0.008-0.027 μg g-1 in Anabas testudineus from Loktak Lake in pre-monsoon and post-monsoon seasons. Pesticide residues were detected only in Anabas testudineus (0.002-0.078 μg g-1) in Nambul River, while these were detected only in Channa puctatus (0.001-0.032 μg g-1) in Moirang River. In Nambol River, pesticide concentrations ranged from 0.002-0.026 μg g-1 in Channa punctatus, and from 0.004-0.005 μg g-1 in Anabas testudineus. Among the five pesticides detected, concentrations of dichlorvos residues detected in the present study (0.027 and 0.032 μg g-1 wet weight) exceeded the Codex Alimentarius maximum residue limit (MRL) of 0.01 mg kg-1 for animal tissues. The rest of the compounds were within the MRL. None of the pesticide residues was detected in the two fish species collected from the control or reference site. The present study indicates that pesticide contamination is emerging as a threat to the water quality and aquatic biodiversity of Loktak Lake, which calls for more detailed studies on the extent and magnitude of these threats. [ABSTRACT FROM AUTHOR]

Nowadays, modulating and tuning the lattice strain of nanozymes has emerged as a powerful tool to boost the enzymatic performance of the material for sensitive bioassays. Here, a two-step lattice strain tuning method was adopted to synthesize highly curved, porous, and thin palladium nanosheet assemblies (Pd–H NSAs), serving as oxidase mimics. These nanostructures showed excellent oxidase-like activity due to hydrogen intercalation, enabling rapid electron transfer and substrate accumulation. Utilizing Pd–H NSAs, we designed a sensitive colorimetric platform for detecting acid phosphatase and alkaline phosphatase activity with a limit of detection (LOD) of 0.0032 and 0.0057 U/L, respectively. We also created a simple colorimetric assay for malathion detection, achieving a linear range of 0.1–10 μM and an LOD of 0.014 μM. Moreover, we applied a paper-based smartphone sensing platform for real fruit sample analysis, highlighting the potential of our biosensor assay for environmental pesticide detection. [ABSTRACT FROM AUTHOR]

The design of heterojunctions that mimic natural photosynthetic systems holds great promise for enhancing photoelectric response. However, the limited interfacial space charge layer (SCL) often fails to provide sufficient driving force for the directional migration of inner charge carriers. Drawing inspiration from the electron transport chain (ETC) in natural photosynthesis system, we developed a novel anisotropic dual S‐scheme heterojunction artificial photosynthetic system composed of Bi2O3−BiOBr−AgI for the first time, with Bi2O3 and AgI selectively distributed along the bicrystal facets of BiOBr. Compared to traditional semiconductors, the anisotropic carrier migration in BiOBr overcomes the recombination resulting from thermodynamic diffusion, thereby establishing a potential ETC for the directional migration of inner charge carriers. Importantly, this pioneering bioinspired design overcomes the limitations imposed by the limited distribution of SCL in heterojunctions, resulting in a remarkable 55‐fold enhancement in photoelectric performance. Leveraging the etching of thiols on Ag‐based materials, this dual S‐scheme heterojunction is further employed in the construction of photoelectrochemical sensors for the detection of acetylcholinesterase and organophosphorus pesticides. [ABSTRACT FROM AUTHOR]

Safety problems caused by organophosphorus pesticide (OP) residues are constantly occurring, so the development of new methods for the degradation and detection of OPs is of great scientific significance. In the present study, β-sheet peptides and β-hairpin peptides for catalyzing the hydrolysis of OPs were designed and synthesized. The peptide sequences with the highest hydrolytic activity (EHSGGVTVDPPLTVEHSAG) were screened by investigating the effect of the location of the active sites of the peptide and the peptide's structure on the degradation of OPs. In addition, the relationship between the peptides' conformation and hydrolytic activity was further analyzed based on density functional theory calculations. The noncovalent interactions of the peptides with the OPs and the electrostatic potential on the molecular surface and molecular docking properties were also investigated. It was found that peptides with approximate active amino acids consisting of the catalytic triad and with the hairpin structure had enhanced hydrolytic activity toward the hydrolysis of OPs. To develop an electrochemical sensor technique to detect OPs, the conductive MXene (Ti3C2) material was first immobilized with a caffeic acid monolayer via enediol–metal complex chemistry and then bound with the β-hairpin peptide (EHSGGVTVDPPLTVEHSAG) via carboxy–amine condensation chemistry between the –COOH of caffeic acid and the –NH2 of the peptide to prepare a MXene–peptide composite. Then, the prepared composite was modified on the surface of a glassy carbon electrode to construct an electrochemical sensor for the detection of OPs. The developed technique could be used to monitor OPs within 15 min with a two orders of linear working range and with a detection limit of 0.15 μM. Meanwhile, the sensor showed good reliability for the detection of OPs in real vegetables. [ABSTRACT FROM AUTHOR]

Dengue fever disease is an important health issue in the city of Jeddah, Saudi Arabia. Chemical pesticides play a vital role in dengue control, through combating the mosquito vector Aedes aegypti L. Standard methods recommended by the World Health Organization were applied in the current work to conduct resistance experiments in both adult and larval stages of Ae. aegypti mosquitoes against eight types of pyrethroid and organophosphorus pesticides used in control programs in Jeddah. The results prove that Ae. aegypti is resistant against the pesticides deltamethrin 0.05%, α‐cypermethrin 0.05%, fenitrothion 1% and temephos, is tolerant with some degree of resistance against cyfluthrin 0.15% and λ‐cyhalothrin 0.5%, as well as tolerant against malathion 5% and pirimiphos‐methyl 0.25%. On the other hand, the bacterial insecticide Bacillus thuringiensis ssp. israelensis (Bti) demonstrated high activity against the field strain of Aedes aegypti larvae, with a resistance ratio (RR) of 1.25. In general, we conclude from these findings that the continuous and frequent application of synthetic pesticides induces resistance in mosquitoes against pesticides. This, of course, forces us to reconsider the pesticides currently used in control programs and do our best towards finding alternative means to combat mosquitoes and the diseases that they can transmit. [ABSTRACT FROM AUTHOR]

A procedure is developed for the simultaneous determination of organophosphorus pesticides (OPP) diazinon, dimethoate, omethoate, pirimiphos-methyl, pirimiphos-ethyl, malathion, malaoxon, chlorpyrifos-methyl, and fosalone in medicinal plant raw materials using high-resolution liquid chromatography–mass spectrometry. The procedure uses a rapid method of sample preparation by the extraction of crushed plant materials with acetonitrile. The analysis conditions in the reversed-phase chromatography version are optimized. Determination is carried out by the internal standard method using deuterated standards malathion-d6 and dichlorvos-d6 based on the two most intense ionic reactions specific for each individual OPP. The procedure was tested on an example of plant raw materials—valerian (Rhizomata cum radicibus Valerianae officinalis) rhizomes and roots and validated according to the specificity, linearity, accuracy, analytical range, limit of quantification, precision, and matrix effect parameters. The proposed procedure can be used to determine the indicated OPP in a wide range of concentrations from 0.01 to 10 000 ng/g of raw materials in medicinal and agricultural plant growing. [ABSTRACT FROM AUTHOR]

In this study, a novel, cost-effective, and environmental-friendly acetylcholinesterase (AChE)-based electrochemical biosensor was developed and utilized for paraoxon-ethyl (PE) detection. In this biosensor, cerium oxide (CeO2) and poly(3,4 ethylenedioxythiophene):poly(styrenesulfonate) (PESOT:PSS) modified paper electrode was fabricated by a simple dip-coating method. The synergistic effect of CeO2 and PEDOT:PSS enhance the performance of AChE-based biosensor in terms of sensitivity and selectivity. The electrical conductivity and stability of the fabricated electrode are further improved with the treatment of ethylene glycol (EG). EG decreases the coulombic interactions between PEDOT and PSS molecules, causes polymer chain reorientation, and improves the non-covalent interaction between cellulose molecules and PEDOT, which further leads to higher conductivity. All electrochemical results validate that the biosensor shows good selectivity (Kselectivity < 1), high sensitivity of 52.10 µA/nM, and a low detection limit of 0.12 nM. The accuracy and applicability of the proposed biosensor were also checked with two real samples. All results validate that the fabricated paper electrode can be a promising alternative to other conventional electrodes. [ABSTRACT FROM AUTHOR]

The present work focuses on the detection of dengue virus using a proposed copper (Cu) and black phosphorus (BP)–based SPR sensor. This proposed sensor is capable of detecting normal and infected blood samples containing plasma, platelets and hemoglobin. We studied the performance parameter at optimized Cu layer thickness of the proposed sensor by calculating that the maximum sensitivity is 150.55°/RIU, 226.73°/RIU and 295.58°/RIU at Rmin values with 57 nm, 57 nm and 51 nm thickness of Cu layer for the detection of plasma, platelet and hemoglobin in the blood sample of dengue malaria. The properties of BP combined with the unique plasmonic properties of SPR sensors can result in enhanced interactions between surface plasmons and incident light. These results are intended for improved sensitivity and remarkable figure of merit (FoM). We also calculated the electric field and penetration depth (PD) for the same sample. In this study, the normal and infected blood samples are successfully examined for the performance parameters for the plasma, platelets and hemoglobin. [ABSTRACT FROM AUTHOR]

A quick, easy, cheap, effective, rugged, and safe method was developed for the multi‐residue analysis of pesticides and antibiotics in aquaculture sediment using high‐performance liquid chromatography‐tandem mass spectrometry (HPLC‐MS/MS). The developed method is based on ultrasonic extraction with acetonitrile and phosphate buffer, salting with sodium chloride, and cleaning with dispersive solid‐phase extraction adsorbent using primary secondary amine, C18, and graphitized carbon black, followed by HPLC‐MS/MS detection. We optimized different extraction methods and the ratio of the cleanup adsorbents to achieve good recoveries at three spiking levels that ranged from 60.4% to 114% with a relative standard deviation below 15% (n = 6). For all analytes, except for flufenoxuron, the limits of quantification were between 1 and 5 µg/kg (dry weight). The validated method was successfully applied to real samples collected from 20 aquacultural ponds, confirming the feasibility of the proposed method. The concentrations of the target analytes in the sediments (dry weight) were in the ranges of 2.2–35.0 µg/kg for sulfonamides, 0–409.1 µg/kg for quinolones, 0–6.56 µg/kg for macrolides, and 0–4.9 µg/kg for pesticides. Moreover, the co‐occurrence of pesticides and antibiotics may potentially pose a high risk to sediment‐dwelling organisms in nine out of the 20 investigated locations. [ABSTRACT FROM AUTHOR]

Current label-free surface-enhanced Raman spectroscopy (SERS) assay for the detection and analysis of organophosphorus pesticides has achieved initial success, but the application still faces constraints of substrate portability and specificity. To this end, this paper demonstrates a method for portable, rapid, and specific detection of low concentrations of fenthion pesticides based on a solid substrate of gold nanoparticle monolayers combined with molecularly imprinted polymers (MIPs). The nano-monolayers were transferred to the surface of mercapto-silicon wafers by interfacial self-assembly technique to form a stable connection with S–Au bonds and, at the same time, prevent nanoparticles from dropping off during the surfactant removal process. Then, the fenthion MIPs were directly generated on the surface of the monolayer film by spin-coating with a pre-polymerization solution and ultraviolet-induced polymerization. Tests showed that the molecular imprint was able to accurately bind to fenthion, but not other molecules, in a mixture of structural analogs, achieving a low concentration detection of 10–8 mol/L. The composite substrate maintained a signal uniformity of a relative standard deviation (RSD) = 7.05% and a batch-to-batch reproducibility of RSD = 10.40%, making it a potential pathway for the extended application of SERS technology. [ABSTRACT FROM AUTHOR]

The excessive use of pesticides in agriculture and the widespread use of metals in industrial activities and or technological applications has significantly increased the concentrations of these pollutants in both aquatic and terrestrial ecosystems worldwide, making aquatic biota increasingly vulnerable and putting many species at risk of extinction. Most aquatic habitats receive pollutants from various anthropogenic actions, leading to interactions between compounds that make them even more toxic. The aim of this study was to assess the effects of the compounds Chlorpyrifos (insecticide) and Cadmium (metal), both individually and in mixtures, on the cladocerans Ceriodaphnia rigaudi and Ceriodaphnia silvestrii. Acute toxicity tests were conducted for the compounds individually and in mixture, and an ecological risk assessment (ERA) was performed for both compounds. Acute toxicity tests with Cadmium resulted in EC50-48 h of 0.020 mg L−1 for C. rigaudi and 0.026 mg L−1 for C. silvestrii, while tests with Chlorpyrifos resulted in EC50-48 h of 0.047 μg L−1 and 0.062 μg L−1, respectively. The mixture test for C. rigaudi showed the occurrence of additive effects, while for C. silvestrii, antagonistic effects occurred depending on the dose level. The species sensitivity distribution curve for crustaceans, rotifers, amphibians, and fishes resulted in an HC5 of 3.13 and an HC50 of 124.7 mg L−1 for Cadmium; an HC5 of 9.96 and an HC50 of 5.71 μg L−1 for Chlorpyrifos. Regarding the ERA values, Cadmium represented a high risk, while Chlorpyrifos represented an insignificant to a high risk. [ABSTRACT FROM AUTHOR]

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Oximes, belonging to imines with the general formula of RR'C=NOH, are produced by the nucleophilic addition reaction between hydroxylamine with ketones or aldehydes, yielding corresponding aldoxime and ketoxime. The presence of hydrogen bond acceptor and donor is the classical feature of oxime‐containing structural framework. This review presents a summary of the role of oximes and its structure activity relationships including antimicrobial, anticancer, anti‐inflammatory, antihyperglycemic, insecticidal agents, along with their involvement in the treatment of organophosphorus poisoning. The review also focused on the pharmacological profile of lead molecules of several classes of oxime‐containing compounds. [ABSTRACT FROM AUTHOR]

Objective: To investigate any connections between urinary organophosphorus pesticide (OPP) metabolites and adiposity measures. Methods: In this study, data from the National Health and Nutrition Examination Survey (NHANES) projects from 2003 to 2008, 2011 to 2012, and 2015 to 2018 were analysed. Obesity was defined as a body mass index (BMI) of 30 kg/m² or higher. Abdominal obesity was defined as a waist circumference (WC) over 102 cm for men and 88 cm for women. Four urinary OPP metabolites (dimethyl phosphate [DMP], diethyl phosphate [DEP], dimethyl phosphorothioate [DMTP], and diethyl phosphorothioate [DETP]) and adiposity measures were examined using multiple linear regression and logistic regression analyses. The correlations between a variety of urinary OPP metabolites and the prevalence of obesity were investigated using weighted quantile sum regression and quantile g-computation regression. Results: In this analysis, a total of 9,505 adults were taken into account. There were 49.81% of male participants, and the average age was 46.00 years old. The median BMI and WC of the subjects were 27.70 kg/m2 and 97.10 cm, respectively. Moreover, 35.60% of the participants were obese, and 54.42% had abdominal obesity. DMP, DMTP, and DETP were discovered to have a negative correlation with WC and BMI in the adjusted models. DMP (OR = 0.93 [95% CI: 0.89–0.98]), DEP (OR = 0.94 [95% CI: 0.90–0.99]), DMTP (OR = 0.91 [95% CI: 0.86–0.95]), and DETP (OR = 0.85 [95% CI: 0.80–0.90]) exhibited negative associations with obesity prevalence. Similar correlations between the prevalence of abdominal obesity and the urine OPP metabolites were discovered. Moreover, the mixture of urinary OPP metabolites showed negative associations with adiposity measures, with DMTP and DETP showing the most significant effects. Conclusion: Together, higher levels of urinary OPP metabolites in the urine were linked to a decline in the prevalence of obesity. [ABSTRACT FROM AUTHOR]

A deep eutectic solvent (DES) with the ability to change from hydrophilic to hydrophobic was designed and synthesized and applied to the determination of organophosphorus (OPP) pesticides in honeysuckle dew samples. Choline chloride, phenol, and tetrahydrofuran (THF) were used as the hydrogen bond acceptor, hydrogen bond donor, and demulsifier, respectively. Eight OPP pesticides were extracted by DES coupled with ultrasonic-assisted extraction (UA) and then chromatographed by GC-MS. DES used as an extract solvent has the advantages of high extraction efficiency, low cost, and environmental protection. Furthermore, DES is compatible with GC-MS. The single factor experiment design and Box–Behnken design (BBD) were applied to the optimization of experimental factors, including the type and composition of extraction solvent, type of demulsifier solvent, the volume of DES and THF, pH of sample solution, and ultrasonic time. Under the optimum experimental conditions, the high degree of linearity from 0.1 to 20.0 ng mL−1 (R2 ≥ 0.9989), the limits of detection from 0.014 to 0.051 ng mL−1 (S/N = 3), and the recoveries of analytes from 81.4 to 104.4% with relative standard deviation below 8.6%. In addition, the adsorption mechanism of OPPs on DES was explored by adsorption kinetic studies. These results have demonstrated that the present method has offered an effective, accurate, and sensitive methodology for OPP pesticides in honeysuckle dew samples, and this method provides a reference for the detection of pesticide residues in traditional Chinese medicine. [ABSTRACT FROM AUTHOR]

An analytical method was established for the simultaneous determination of 29 pesticides in litchi by a high-performance liquid chromatography-tandem quadrupole-time of flight-mass spectrometry (HPLC-Q-TOF/MS) technique combined with an optimized QuEChERS procedure. The samples were extracted by acetonitrile and the acetonitrile supernatant was collected for purification after salting-out (magnesium sulfate anhydrous and sodium chloride) and centrifugation.Under the optimized chromatographic and mass spectrometric conditions, the data were collected by electrospray ionization (ESI) sources in positive and negative ion modes. The calibration curves of 29 pesticides showed good linearity in a concentration range of 0.001-0.2 mg/L (R²>0.99). The average recoveries were 70.2%-102.4% at three spiked levels (0.01, 0.1, 0.50 mg/kg), while the relative standard deviations (RSD) were 2.4%-6.2%. The limits of detection and limits of quantification ranged from 0.1 μg/kg to 3 μg/kg and 0.3 μg/kg to 10 μg/kg, respectively. This method was a simple and efficient method with high sensitivity and precision and had practical value for the rapid detection of residues of 29 pesticides in litchi. [ABSTRACT FROM AUTHOR]

The removal of organophosphorus pesticides is the growing concern. The pesticides are biomagnified in food chain, causing greater health hazards to humans and animals. Adsorption is one of the most efficient approaches for removal of organophosphorus compounds. The current study describes the adsorptive removal of phosmet by silylated graphene oxide (sGO). The adsorption study was performed by batch adsorption method by varying pH, temperature, dosage, contact time, etc. The isotherm studies were also performed to reveal the nature of adsorption. The mechanism of adsorption of phosmet was studied on synthesized and well-characterized sGO. The functionalized derivative of graphene oxide, sGO, has improved biocompatibility and removal efficiency against phosmet. The phenomenon of adsorption is dominantly chemi-physiosorption as suggested from Freundlich isotherm and pseudo-second-order kinetics. The thermodynamics studies further showed that the negative enthalpy and negative Gibb's free energy is indicative of feasibility of adsorption by chemisorption mechanism. The pH studies indicated that the adsorption of sGO on phosmet was highest at neutral as well as basic pH. Finally, the regeneration studies showed that the adsorbent can be utilized till five cycles, where the efficiency is reduced to 50%. Thus, the complete study gives an account of effective removal of phosmet using sGO as an adsorbent by chemisorption involving pi–pi interaction, hydrogen bonding, and electrostatic forces as major interactive forces. [ABSTRACT FROM AUTHOR]

In this study, the goal was to develop a method for detecting and classifying organophosphorus pesticides (OPPs) in bodies of water. Sixty-five samples with different concentrations were prepared for each of the organophosphorus pesticides, namely chlorpyrifos, acephate, parathion-methyl, trichlorphon, dichlorvos, profenofos, malathion, dimethoate, fenthion, and phoxim, respectively. Firstly, the spectral data of all the samples was obtained using a UV–visible spectrometer. Secondly, five preprocessing methods, six manifold learning methods, and five machine learning algorithms were utilized to build detection models for identifying OPPs in water bodies. The findings indicate that the accuracy of machine learning models trained on data preprocessed using convolutional smoothing + first-order derivatives (SG + FD) outperforms that of models trained on data preprocessed using other methods. The backpropagation neural network (BPNN) model exhibited the highest accuracy rate at 99.95%, followed by the support vector machine (SVM) and convolutional neural network (CNN) models, both at 99.92%. The extreme learning machine (ELM) and K-nearest neighbors (KNN) models demonstrated accuracy rates of 99.84% and 99.81%, respectively. Following the application of a manifold learning algorithm to the full-wavelength data set for the purpose of dimensionality reduction, the data was then visualized in the first three dimensions. The results demonstrate that the t-distributed domain embedding (t-SNE) algorithm is superior, exhibiting dense clustering of similar clusters and clear classification of dissimilar ones. SG + FD-t-SNE-SVM ranks highest among the feature extraction models in terms of performance. The feature extraction dimension was set to 4, and the average classification accuracy was 99.98%, which slightly improved the prediction performance over the full-wavelength model. As shown in this study, the ultraviolet–visible (UV–visible) spectroscopy system combined with the t-SNE and SVM algorithms can effectively identify and classify OPPs in waterbodies. [ABSTRACT FROM AUTHOR]