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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 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]

ABSTRACT 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]

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]

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]

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 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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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]

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]

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]

A recent study showed the potential of the DA Perten 7200 NIR Spectrometer in detecting chlorpyrifos-methyl pesticide residue in rough, brown, and milled rice. However, this instrument is still lab-based and generally suited for point-of-sale testing. To provide a field-deployable version of this technique, an existing light emitting diode (LED)-based instrument that provides discrete NIR wavelength illumination and reflectance spectra over the range of 850–1550 nm was tested. Spectra were collected from rough, brown, and milled rice at different pesticide concentrations and analyzed for quantitative and qualitative measurement using partial least squares regression (PLS) and discriminant analysis (DA). Simulations for two LED-based instruments were also evaluated using corresponding segments of spectra from the DA7200 to represent LED illumination. For the simulation of the existing LED-based instrument (LEDPrototype1) fitted with 850, 910, 940, 970, 1070, 1200, 1300, 1450, and 1550 nm LED wavelengths, resulting R2 ranged from 0.52 to 0.71, and the correct classification was 70.4% to 100%. The simulation of a second LED instrument (LEDPrototype2) fitted with 980, 1050, 1200, 1300, 1450, 1550, 1600, and 1650 nm LED wavelengths showed R2 of 0.59 to 0.82 and correct classifications of 66% to 100%. These LED wavelengths were selected based on the significant wavelength regions from the PLS regression coefficients of DA7200 and the commercial availability of LED wavelengths. Results showed that it is possible to use a multi-spectral LED-based instrument to detect varying levels of chlorpyrifos-methyl pesticide residue in rough, brown, and milled rice. [ABSTRACT FROM AUTHOR]

We report on the sensing of a hazardous pesticide alphacypermethrin (ACM) using electrochemical technique through a nanocomposite film modified electrode. The nanocomposite film comprising of octadecylamine, chitosan, polyvinyl alcohol-silver nanowires and haemoglobin, shortly (OCPAH), was prepared by Langmuir–Blodgett (LB) film deposition technique on various substrates and electrodes. The composite LB film was characterised by UV-visible spectroscopy and scanning electron microscopy, which confirms the stable and multilayer film. The LB film modified electrode was used for sensing ACM pesticide by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and square wave voltammetry (SWV) techniques. The achieved sensing parameters such as limit of detection as 14 nM, 5 nM and 10 nM; linear range as 10–100 nM, 10–40 nM and 50–100 nM/10–100 nM; and sensitivity as 0.418 µA/nM/cm2, 0.259 µA/nM/cm2 and 0.271 µA/nM/cm2 for CV, DPV and SWV techniques, respectively. The reported sensor is found to have stability of 74% upto 20 cycles, the relative standard deviation (RSD) value for metal ion/organic interference species as 2% and for real samples are within 1.4% using CV technique. The reported nanocomposite-based ACM pesticide sensor will open up new options for research on LB film nanocomposite-based sensing of different organophosphorus groups of pesticides. [ABSTRACT FROM AUTHOR]

A colorimetric analysis platform has been successfully developed based on FeCo-NC dual-atom nanozyme (FeCo-NC DAzyme) for the detection of organophosphorus pesticides (OPPs). The FeCo-NC DAzyme exhibited exceptional oxidase-like activity (OXD), enabling the catalysis of colorless TMB to form blue oxidized TMB (oxTMB) without the need for H2O2 involvement. By combining acid phosphatase (ACP) hydrolase with FeCo-NC DAzyme, a "FeCo-NC DAzyme + TMB + ACP + SAP" colorimetric system was constructed, which facilitated the rapid detection of malathion. The chromogenic system was applied to detect malathion using a smartphone-based app and an auxiliary imaging interferogram device for colorimetric measurements, which have a linear range of 0.05–4.0 µM and a limit of detection (LOD) as low as 15 nM in real samples, comparable to UV-Vis and HPLC-DAD detection methods. Overall, these findings present a novel approach for convenient, rapid, and on-site monitoring of OPPs. [ABSTRACT FROM AUTHOR]

Purpose: This study aimed to investigate the residual levels of representative organophosphorus and pyrethroid pesticides (chlorpyrifos, cypermethrin, deltamethrin, and lambda-cyhalothrin) in agricultural soils and crops in Shaanxi Province, and to reveal their accumulation characteristics and regional distribution characteristics in crops. Materials and methods: The study was conducted using 115 soils and crops samples from typical agricultural areas in Shaanxi Province. The pesticide residues were measured using gas chromatography-mass spectrometry (GC-MS). The crops were analyzed based on the residue characteristics of fruits, vegetables, and field crops. Additionally, the pesticide residues in crops from the Guanzhong area (central part of Shaanxi), northern Shaanxi, and southern Shaanxi regions were analyzed. A correlation analysis was conducted to examine the influencing factors of pesticide residues in soil-crops, considering the physical and chemical properties of the soil in Shaanxi Province. Results and discussion: The results indicate that there are differences in the detection rates and residual concentrations of different pesticides in soil. In the Guanzhong area, the pesticide residual levels in crops follow the trend of chlorpyrifos > deltamethrin > lambda-cyhalothrin > cypermethrin, with relatively high pesticide residues found in corn. In northern Shaanxi, the overall pesticide residual levels in crops show a trend of chlorpyrifos > deltamethrin > cypermethrin > lambda-cyhalothrin. In southern Shaanxi, all the pesticides were detected to varying degrees in crops, with chlorpyrifos showing the highest residual levels. Conclusions: All four pesticides were detected in the soils of the study area and the enrichment capacity of different crops varied greatly. Pesticide enrichment is not only affected by temperature and climate conditions in different regions, but soil organic matter, pH, and CEC also have a significant effect on the enrichment of pesticides by crops. [ABSTRACT FROM AUTHOR]

The physiological and molecular responses of leukocytes are altered by organophosphate pesticides. Some reports have shown that diazinon causes immunotoxic effects; diazoxon, the oxon metabolite of diazinon, is attributed to influence the immune response by affecting the leukocyte cholinergic system. In this study, the in vitro effects of diazoxon on molecules involved in cell signaling (cAMP, IP3, DAG, JAK1, and STAT3), which play a crucial role in the activation, differentiation, and survival of leukocytes, were evaluated. Data indicate that diazoxon leads to a decrease in cAMP concentration and an increase in basal IP3 levels. However, diazoxon does not affect basal levels of JAK1 and STAT3 phosphorylation. Instead, diazoxon inhibits leukocyte responsiveness to phorbol myristate acetate and ionomycin, substances that, under normal conditions, enhance JAK/STAT signaling. These findings demonstrate that diazoxon significantly affects key molecular parameters related to cell signaling. [ABSTRACT FROM AUTHOR]

MPs have raised significant public concern due to their role as carriers of organic contaminants in aqueous solutions. DZN is a non-systemic organophosphorus pesticide that poses risks to human and environmental health. This study aimed to investigate the adsorption of DZN onto PE MPs by examining factors such as PE dose, reaction time, pesticide concentration, and pH through experimental runs based on the Box‒Behnken model. According to the Langmuir model, the maximum adsorption capacity of PE for DZN was 0.35 mg/g. The results indicated that the highest adsorption rate of DZN (92%) was observed in distilled water, while the lowest adsorption rate (57%) was observed in municipal wastewater. The ΔH° and ΔS° values were obtained as − 0.16 kJ/mol and 54.41 J/(mol K), respectively. Therefore, regarding negative ΔG° values, it can be concluded that the adsorption of DZN onto PE MPs is an exothermic, highly disordered, and spontaneous process. The findings indicate a reduction in the adsorption rate of DZN as the concentrations of interfering compounds increase. These findings offer understanding of the interaction between MPs and organic contaminants, emphasizing the need for further studies and approaches to reduce their harmful impact on human health and the environment. [ABSTRACT FROM AUTHOR]

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Background: Pesticide poisoning kills hundreds of thousands of people in the Asia Pacific region each year. The majority are from deliberate self-poisoning with organophosphorus pesticides (OP), paraquat etc. It is a critical health problem in rural areas, where hazardous pesticides are easily available. Very few studies were present regarding this in India and research on anti-dotes to commonly available pesticides is very minimal. According to WHO report, it is the 2nd most common cause of death among people aged 15-29 years. Methodology: An observational study was conducted to study suicidal poisoning cases from Jan-June 2022 in a retrospective record-based manner. Qualitative variables were represented with graphs and tables. Quantitative variables were represented with mean and Standard deviation. Multinomial logistic regression was done to test the significance of poisoning agents with survival status. Nagelkerke R-squared mean regression model was considered in the analysis. p-value less than 0.05 was considered significant. Results: The incidence of suicidal poisoning was 696(~0.46%) during the study period. The mean age of the study population is 32.5±12.3 years. Majority of the cases were Organophosphorus compounds and paraquat comprising a total of about 26.11%. Fatality rate was 17.4% Multinomial logistic regression of various poisoning agents showed high significance of mortality OP poisoning (p=0.03), Paraquat poisoning (p<0.001) and Herbicides (p=0.02). Conclusion: Young populations were more prone to commit suicide suggesting increased recognition of the need for a coordinated response involving public health officials and psychiatric specialists to conduct mental health awareness camps and to provide counselling. Strengthening of translational research to develop anti-dotes for commonly available pesticides. [ABSTRACT FROM AUTHOR]

BACKGROUND: Several studies have addressed the adsorption of pesticides such as alachlor, acetochlor, metolachlor and fenthion from water and wastewater, yet the interaction of these compounds with natural organic matter (NOM) complicates their effective removal owing to competitive adsorption effects. This study aims to fill this gap by exploring the efficacy of nitric acid and chlorosulfonic acid‐modified activated carbons (ACs) in removing both pesticides and NOM under realistic environmental conditions. RESULTS: Modifications using nitric acid and chlorosulfonic acid significantly improved the pesticide removal capabilities of Norit SX F Cat (AC1) adsorbents. While both the original and chlorosulfonic acid‐modified adsorbents showed comparable efficacy in pesticide removal, nitric acid‐modified AC Puriss (AC2) adsorbents were less effective. Remarkably, a 100 mg L−1 dose of both original and modified powdered ACs (PACs) removed >98% of all four pesticides from water samples. Additionally, a lower 25 mg L−1 dose effectively achieved similar removal rates, demonstrating their utility as feasible options for water treatment. CONCLUSION: Modifying PACs with nitric acid and chlorosulfonic acid has been proven to enhance their structural and adsorptive properties significantly. These modifications led to improved pesticide removal efficiencies, particularly with the chlorosulfonic acid‐modified PACs, which demonstrated superior performance in adsorption tests. The study also highlighted the competitive adsorption posed by low‐molecular‐weight organic substances in water, which compete with pesticides for active adsorption sites. © 2024 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI). [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]

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]

Abstract Background Organophosphorus 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. Methods We 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. Results OP 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. Conclusion In 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.

The rapid and efficient identification and quantification of neurotoxic organophosphorus pesticides (OPs) are crucial for ensuring environmental safety and human health. However, the current acetylcholinesterase OP sensors are largely limited by the stability and cost of bio-enzymes, as well as the occurrence of false negatives in "signal-off" strategies. In this study, we present a pioneering approach that utilizes high-performance electrochemiluminescence (ECL) of tungsten disulfide quantum dots (WS2 QDs) to develop an alternative sustainable non-enzymatic ECL sensor for "signal-on" OP detection. The presence of phosphate esters in OPs efficiently mediates ECL enhancement of WS2 QDs using K2S2O8 as a coreactant. With this new strategy, we achieved highly sensitive and selective detection of common OPs, including methyl parathion, naled, dimethoate, and malathion, with detection limits of 1.48 pg mL−1, 4.30 pg mL−1, 0.35 pg mL−1, and 5.58 pg mL−1, respectively. When applied to river water and spinach samples, the sensor also demonstrated high reproducibility and good recovery. The electrochemical hydrolysis decomposition of OPs during the detection process in this study provides a "two birds with one stone" strategy, serving the dual objective of identifying and degrading OPs. This work paves a new avenue for direct ECL sensing in environmental and food screening, eliminating the reliance on common indirect biological identification elements. [ABSTRACT FROM AUTHOR]

Chlorpyrifos is an endocrine disruptor pesticide that induces breast cancer cell proliferation through Estrogen receptor alpha pathway in humans. It also has toxic effects on some beneficial insects like bees, wasps, and arthropods, even low levels of CP can kill fish in water. Thus, it is important to efficiently remove this compound from wastewaters to get rid of its hazardous effects. Al2O3 supported ZnO.MoO3 composite was prepared as an efficient material for photo‐degradation of chlorpyrifos under UV irradiation and characterized by SEM‐EDX, XRD and TG techniques. The XRD analysis showed the orthorhombic structures with band gap of 2.86 eV for ZnO.MoO3/Al2O3 which was 2.96 eV for MoO3/Al2O3. The kinetics of degradation depicted that ZnO.MoO3/Al2O3 afforded a complete degradation of chlorpyrifos with half life of only 3 minutes which otherwise was 24 minutes in the presence of MoO3/Al2O3. The complete mineralization of chlorpyrifos was confirmed by GC/MS analysis, where no peaks of intermediates were recorded. The prepared material also exhibited good recyclability without any leaching of Zn and Mo metals. Thus, ZnO.MoO3/Al2O3 is an efficient and cost effective material for removal of chlorpyrifos. Its potential may also be explored for the removal of other hazardous organic pollutants. [ABSTRACT FROM AUTHOR]

Chlorpyrifos is an endocrine disruptor pesticide that induces breast cancer cell proliferation through Estrogen receptor alpha pathway in humans. It also has toxic effects on some beneficial insects like bees, wasps, and arthropods, even low levels of CP can kill fish in water. Thus, it is important to efficiently remove this compound from wastewaters to get rid of its hazardous effects. Al2O3 supported ZnO.MoO3 composite was prepared as an efficient material for photo‐degradation of chlorpyrifos under UV irradiation and characterized by SEM‐EDX, XRD and TG techniques. The XRD analysis showed the orthorhombic structures with band gap of 2.86 eV for ZnO.MoO3/Al2O3 which was 2.96 eV for MoO3/Al2O3. The kinetics of degradation depicted that ZnO.MoO3/Al2O3 afforded a complete degradation of chlorpyrifos with half life of only 3 minutes which otherwise was 24 minutes in the presence of MoO3/Al2O3. The complete mineralization of chlorpyrifos was confirmed by GC/MS analysis, where no peaks of intermediates were recorded. The prepared material also exhibited good recyclability without any leaching of Zn and Mo metals. Thus, ZnO.MoO3/Al2O3 is an efficient and cost effective material for removal of chlorpyrifos. Its potential may also be explored for the removal of other hazardous organic pollutants. [ABSTRACT FROM AUTHOR]

The identification and detection of pesticides is crucial to protecting both the environment and human health. However, it can be challenging to conveniently and rapidly differentiate between different types of pesticides. We developed a supramolecular fluorescent sensor array, in which calixarenes with broad-spectrum encapsulation capacity served as recognition receptors. The sensor array exhibits distinct fluorescence change patterns for seven tested pesticides, encompassing herbicides, insecticides, and fungicides. With a reaction time of just three minutes, the sensor array proves to be a rapid and efficient tool for the discrimination of pesticides. Furthermore, this supramolecular sensing approach can be easily extended to enable real-time and on-site visual detection of varying concentrations of imazalil using a smartphone with a color scanning application. This work not only provides a simple and effective method for pesticide identification and quantification, but also offers a versatile and advantageous platform for the recognition of other analytes in relevant fields. [ABSTRACT FROM AUTHOR]

Wearing appropriate personal protective equipment (PPE) for spraying pesticides is one of the methods to reduce dermal exposure to toxic pesticides. The main issues with such PPEs are comfortability and durable functionality. These issues were addressed by developing a bi-layer fabric treated with functionalized iron molybdate (Fe2(MoO4)3) nanoparticles (NPs). Three structures of bi-layer fabrics were developed to get the most comfortable fabric one with an upper layer of cotton (1*1 woven) and an underlayer of polyester (3/1 twill weave). The Fe2(MoO4)3 NPs were synthesized and functionalized with two silanes, i.e., Octadecyltrimethoxysilane and 1,2 Bis(triethoxysilyl)ethane. Fourier transform-infrared spectroscopy and thermogravimetric analysis were done to confirm the binding of silanes with NPs. Functionalized Fe2(MoO4)3 NPs were coated on selected fabric by dip-dry coating, and surface topography was assessed by Scanning Electron Microscopy (SEM). The water contact angle of 151° was exhibited by modified fabric. The photocatalysis of Benzoepin (C9H6Cl6O3S) by Fe2(MoO4)3 NPs under visible light was 75%. The UPF values obtained were 55 and 50 before and after washing, respectively. The developed superhydrophobic fabric could be efficiently used for durable pesticide-resistant clothing because the pesticide would not be adsorbed/absorbed by the fabric. If absorbed it could be possibly degraded by Fe2(MoO4)3 NPs rescuing the wearer from the hazardous effects of pesticides as well as UV rays. [ABSTRACT FROM AUTHOR]

Background: The aim of the study was to develop a technique for quantitative determination of rat urine metabolites by HPLC–MS/MS, which can be used to search for biomarkers of acute intoxication with organophosphates (OPs). Results: The content of metabolites in the urine of rats exposed to a single dose of paraoxon (POX1x); interval, twice daily administration of paraoxon (POX2x); exposure to 2-(o-cresyl)-4H-1, 3, 2-benzodioxaphosphorin-2-oxide and paraoxon (CBPOX) was investigated. New data were obtained on the content in the urine of intact rats as well as rats in 3 models of OP poisoning: 3-methylhistidine, threonine, creatine, creatinine, lactic acid, acetylcarnitine, inosine, hypoxanthine, adenine, 3-hydroxymethyl-butyrate and 2-hydroxymethyl-butyrate. Conclusions: The proposed assay procedure is a simple and reliable tool for urine metabolomic studies. Within 1–3 days after OP exposure in all three models of acute intoxication, the concentration of metabolites in rat urine, with the exception of adenine, changes similarly and symmetrically, regardless of the method of poisoning modeling, in all three models of acute intoxication. Further studies are needed to determine the specificity and reliability of using urinary metabolite concentration changes as potential biomarkers of acute organophosphate intoxication. [ABSTRACT FROM AUTHOR]

Fast and simple detection of toxic compounds in aqueous solutions is important for agriculture and pollution monitoring. Enzyme‐based electrochemical biosensors are a promising platform for this task, but they usually lack the ability to distinguish between toxicants if more than one toxicant is present in the sample. Herein, we propose a new method of detection of various toxic compounds in complex multi‐component water samples using an electrochemical biosensor and additional stages of enzyme reactivation. The biosensor is based on butyrylcholinesterase immobilized on the surface of conductometric transducers using glutaraldehyde cross‐linking. It was shown that the biosensor is sensitive to organophosphorus pesticides, heavy metals ions, glycoalkaloids, but has a limited sensitivity to mycotoxins and surfactants. We propose a procedure for the analysis of complex samples with several reactivation stages to be able to determine which category of toxicants is present. Glycoalkaloids are reversible inhibitors and biosensor's activity is restored by washing in working buffer; heavy metal ions and pesticides are irreversible inhibitors and biosensor's activity is restored by incubation in EDTA and PAM‐2 solutions, correspondingly. This biosensor can be used for the detection of separate toxicants or for analysis of their mixtures in aqueous samples. It can be also used for the evaluation of total toxicity of the samples and applied for water quality monitoring. [ABSTRACT FROM AUTHOR]

Despite the negative effects that the use of pesticides (such as herbicides and insecticides) have on human health and water resources, a significant portion of the world's agricultural production depends on them. The purpose of this study was to determine selected residual concentrations of pesticides (diazinon, ethion, malathion, alachlor, methyl-parathion, trifluralin, atrazine, chlorpyrifos, and azinphosmethyl) in samples from Shiraz potable water sources. For this purpose, water treatment plant, groundwater wells, treated surface water, and a mixture of groundwater and treated surface water were taken. In addition, statistical and risk analyses (carcinogenic and non-carcinogenic) were used. According to the results, chlorpyrifos with 84.4% had the highest removal efficiency and methyl-parathion with 10% had the lowest removal rate in the Shiraz water treatment plant process. The highest mean concentration was related to azinphos- methyl (1.5 μg/L) and chlorpyrifos (0.59 μg/L) in the groundwater samples. All measured compounds in water source samples were below standard levels, except for chlorpyrifos and azinphos-methyl, which were reported in groundwater above the limit recommended by the Environmental Protection Agency (EPA). The results showed that while the selected pesticides measured had a low non-carcinogenic risk for both adults and children, malathion and trifluralin posed a high carcinogenic risk for adults. [ABSTRACT FROM AUTHOR]

Globally, people are in great threat due to the highly spreading of viral infectious diseases. Every year like 100–300 million cases of infections are found, and among them, above 80% are not recognized and irrelevant. Dengue virus (DENV) is an arbovirus infection that currently infects people most frequently. DENV encompasses four viral serotypes, and they each express comparable sign. From a mild febrile sickness to a potentially fatal dengue hemorrhagic fever, dengue can induce a variety of symptoms. Presently, the globe is being challenged by the untimely identification of dengue infection. Therefore, this review summarizes advances in the detection of dengue from conventional methods (nucleic acid‐based, polymerase chain reaction‐based, and serological approaches) to novel biosensors. This work illustrates an extensive study of the current designs and fabrication approaches involved in the formation of electrochemical biosensors for untimely identifications of dengue. Additionally, in electrochemical sensing of DENV, we skimmed through significances of biorecognition molecules like lectins, nucleic acid, and antibodies. The introduction of emerging techniques such as the CRISPR/Cas' system and their integration with biosensing platforms has also been summarized. Furthermore, the review revealed the importance of electrochemical approach compared with traditional diagnostic methods. [ABSTRACT FROM AUTHOR]

The idea of this study was the estimation of the theoretical acute toxicity (t-LD50, rat, oral dose) of organophosphorus-based chemical warfare agents from the G-series (n = 12) using different in silico methods. Initially identified in Germany, the G-type nerve agents include potent compounds such as tabun, sarin, and soman. Despite their historical significance, there is a noticeable gap in acute toxicity data for these agents. This study employs qualitative (STopTox and AdmetSAR) and quantitative (TEST; CATMoS; ProTox-II and QSAR Toolbox) in silico methods to predict LD50 values, offering an ethical alternative to animal testing. Additionally, we conducted quantitative extrapolation from animals, and the results of qualitative tests confirmed the acute toxicity potential of these substances and enabled the identification of toxicophoric groups. According to our estimations, the most lethal agents within this category were GV, soman (GD), sarin (GB), thiosarin (GBS), and chlorosarin (GC), with t-LD50 values (oral administration, extrapolated from rat to human) of 0.05 mg/kg bw, 0.08 mg/kg bw, 0.12 mg/kg bw, 0.15 mg/kg bw, and 0.17 mg/kg bw, respectively. On the contrary, compounds with a cycloalkane attached to the phospho-oxygen linkage, specifically methyl cyclosarin and cyclosarin, were found to be the least toxic, with values of 2.28 mg/kg bw and 3.03 mg/kg bw. The findings aim to fill the knowledge gap regarding the acute toxicity of these agents, highlighting the need for modern toxicological methods that align with ethical considerations, next-generation risk assessment (NGRA) and the 3Rs (replacement, reduction and refinement) principles. [ABSTRACT FROM AUTHOR]

Oral squamous cell carcinoma (OSCC) remains a significant global challenge in the medical field, accounting for approximately 300,000 incidences and 145,000 mortalities annually. Studies suggest that early cancer detection is the most vital factor in improving OSCC patient outcomes. Effective clinical diagnosis methods for early OSCC are needed urgently. OSCC biomarkers are identified to be associated with cancer progression and biosensors are devices developed to detect the presence of OSCC biomarkers to allow early cancer diagnosis. Biosensor technology has significant potential in providing rapid and accurate detection of OSCC biomarkers with high sensitivity and specificity. Biosensors have various advantages compared to conventional diagnostic methods such as being non-invasive, low-cost, and convenient. Biosensors hold the potential to be adopted as point-of-care-testing (POCT) devices by bringing biosensor technology to the patients. This review aims to provide a comprehensive review by describing and comparing different categories of OSCC biosensors based on their advantages and drawbacks. The recent obstacles and opportunities for developing effective biosensors for cancer diagnosis are summarized. • Oral squamous cell carcinoma (OSCC) remains a significant global challenge. • Effective clinical diagnosis methods for early OSCC are needed urgently. • OSCC biomarkers are identified to be associated with cancer progression. • Biosensors are devices developed to detect the presence of OSCC biomarkers. • This review described and compared different categories of OSCC biosensors. [ABSTRACT FROM AUTHOR]

A novel electrochemical sensor, MIP/Cu-MOF/rGO/AuNPs/GCE, was developed by depositing gold nanoparticles, coating Cu-MOF/GO on the surface of glassy carbon electrode (GCE) before electroreducing graphene oxide (GO) to rGO and covering molecularly imprinted membrane by electropolymerization for highly sensitive detection of electroneutral organophosphorus pesticide residues in agricultural product. Cyclic voltammetry, differential pulse voltametry, scanning electron microscopy, energy-dispersive spectroscopy, and atomic force microscopy were used to characterize the imprinted sensor. Several key factors such as chitosan concentration, suspension volume, pH of polymerization solution, and polymerization scanning rate during preparation of the imprinted sensor were optimized in detail. When electroneutral phosmet was used as a template, the linear range of MIP/Cu-MOF/rGO/AuNPs/GCE for detecting phosmet was 1.00 × 10−14–5.00 × 10−7 mol/L with the limit of detection of 7.20 × 10−15 mol/L at working potentials of − 0.2 to 0.6 V. The selectivity, reproducibility, and repeatability of MIP/Cu-MOF/rGO/AuNPs/GCE were all acceptable. The recoveries of this method for determining phosmet in real samples ranged from 94.2 to 106.5%. The MIP/Cu-MOF/rGO/AuNPs/GCE sensor could be applied to detect electroneutral pesticide residues in organisms and agricultural products. [ABSTRACT FROM AUTHOR]

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g−1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H2O2-directed transformation of 3,3′,5,5′-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing. [ABSTRACT FROM AUTHOR]

Convenient methods for the synthesis of a series of organophosphorus analogs of glycine containing aminomethyl groups as well as azaheterocyclic and amino acid moieties have been developed. Aminomethylation of phosphinic acid esters with chloro-, alkoxy- and amino-substituted methyl(dialkyl)amines affords various new functionalized aminomethylphosphonites and bis(aminomethyl)phosphinates. The resulting compounds are of interest as promising biologically active substances, extractants, and water-soluble ligands. [ABSTRACT FROM AUTHOR]