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The escalating global demand for food and industrialization has placed significant pressure on the integrity and management of inland lake ecosystems. Herein, the organophosphorus pesticides (OPPs) pollution status and their relationship with dissolved organic matter (DOM) in Dongting Lake were investigated to identify the ecological risks and potential sources of OPPs. The total concentrations of 18 detected OPPs were in the range of 13.49-375.24 ng/L, with higher concentration observed in east and west lake regions. Among these, fenthion was the dominant contributor, accounting for 64% of total OPPs, posing significant ecological risk to aquatic organisms. Nearly all of sites showed high combined risk of total OPPs. Parallel factor analysis (PARAFAC) and fluorescence regional integration (FRI) technique showed that DOM was mainly composed of terrestrial humic-like and tryptophan-like substances. Moreover, correlation analysis revealed a close association between DOM optical parameters and OPP concentrations. Specifically, OPPs exhibited a significantly positive correlation with tyrosine-like substances, while displaying a negative correlation with fulvic acid-like substances. These results indicated that OPP concentrations may decrease with increasing humification levels and declining tyrosine-like substance contents. This study underscores the critical role of DOM in assessing the occurrence and sources of OPPs in aquatic environments, providing valuable insights for effective environmental management strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

An efficient PCN-224/graphene aerogel modified silica (PCN-224/GA@Sil)-based extraction method was established for monitoring the degradation process of two organophosphorus pesticides (OPPs) in juice. PCN-224/GA@Sil exhibited higher surface area (307.35 m 2 g -1 ) than graphene oxide modified silica (254.09 m 2 g -1 ). The introduction of PCN-224 endowed the sorbent with excellent adsorption specificity towards OPPs due to the ZrˑˑˑS/O coordination bond. PCN-224 exhibited relatively higher theoretical adsorption energies of PCN-224 towards fenitrothion and fenthion were 0.68 eV and -0.31 eV. The established PCN-224/GA@Sil-HPLC method showed the linearity of 0.2-500 μg L -1 for analytes. The matrix effects in juice were 9.68 % and 3.61 % for fenitrothion and fenthion. Finally, it was used for the sample pretreatment of juice preventing interference from food matrices to monitor the degradation of two OPPs. A combination method of ultrasound and xenon lamp was adopted to degrade fenitrothion and fenthion displaying the synergistic effect (SE=2.12, 1.39)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The reliable detection of organophosphorus pesticides (OPs) in complex matrices remains an enormous challenge due to inevitable interference of sample matrices and testing factors. To address this issue, we designed a nanozyme-coated mesoporous COF with guest molecule loading, and successfully used it to construct a dual-ratio dual-mode sensor through target-regulated signal generation. The multifunctional COF-based composite (MB/COF@MnO 2 , MCM) featured high loading of methylene blue (MB), oxidase-like MnO 2 coatings as gatekeepers, and specific recognition of thiocholine (TCh). TCh, a regulator produced from acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylthiocholine, could decompose MnO 2 coatings, triggering the release of abundant MB and oxidation of few o-phenylenediamine (OPD). OPs, strong inhibitors of AChE, could restrain TCh production and MnO 2 decomposition, thereby controlling the release of less MB and oxidation of more OPD. This regulation boosted the dual-ratio dual-mode assay of OPs by using the released MB and oxidized OPD in the solution as testing signals, measured by both fluorescent and electrochemical methods. Experimental results demonstrated the sensitive detection of dichlorvos with LODs of 0.083 and 0.026 ng/mL via the fluorescent/electrochemical mode, respectively. This study represented a creative endeavor to develop dual-ratio dual-mode sensors for OPs detection in complex samples, offering high sensitivity, excellent selectivity, and good reliability., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The rapid global population growth since the early 2000s has significantly increased the demand for agricultural products, leading to widespread pesticide use, particularly organophosphorus pesticides (OPPs). This extensive application poses severe environmental risks by contaminating air, soil, and water resources. To protect groundwater quality, it is crucial to understand the transport and fate of these pesticides in soil and sediment. This study investigates the effects of hydrochars and biochars derived from sugar beet shreds (SBS) and Miscanthus×giganteus (MIS) on the retardation and biodegradation of OPPs in alluvial Danube sandy soil. The research is novel in its approach, isolating native OPP-degrading bacteria from natural alluvial sandy soil, inoculating them onto chars, and reapplying these bioaugmented chars to the same soil to enhance biodegradation and reduce pesticide leaching. The amendment of chars with immobilized Bacillus megaterium BD5 significantly increased bacterial abundance and activity. Metabarcoding of the 16S rRNA gene revealed a dominance of Proteobacteria (48.0-84.8 %) and Firmicutes (8.3-35.6 %). Transport modeling showed retardation coefficients (R d ) for OPPs ranging from 10 to 350, with biodegradation rates varying between 0.05 % and 75 %, indicating a positive correlation between retardation and biodegradation. The detection of biodegradation byproducts, including derivatives of phosphin, pyridine, and pyrazole, in the column leachate confirmed that biodegradation had occurred. Additionally, principal component analysis (PCA) revealed positive correlations among retardation, biodegradation, specific surface area (SSA), aldehyde/ketone groups, and bacterial count. These findings demonstrate the potential of biochar and hydrochar amendments to enhance OPP immobilization in contaminated soils, thereby reducing their leaching into groundwater. This study offers a comprehensive approach to the remediation of pesticide-contaminated soils, advancing both our fundamental understanding and the practical applications of environmental remediation techniques., Competing Interests: Declaration of Competing Interest The authors would like to declare that they have no conflicts of interest associated with this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

In this study, a hydrophobic covalent organic framework-functionalized magnetic composite (CoFe 2 O 4 @Ti 3 C 2 @TAPB-TFTA) with a high specific area with 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 2,3,5,6-tetrafluoroterephthalaldehyde (TFTA) was designed and synthesized through Schiff base reaction. An efficient magnetic solid-phase extraction method was established and combined with gas chromatography-triple quadrupole mass spectrometry to sensitively determine 10 organochlorine and organophosphorus pesticides in tea samples. The established method exhibited good linearity in the range of 0.05-120 μg/L and had low limits of detection (0.013-0.018 μg/L). The method was evaluated with tea samples, and the spiked recoveries of pesticides in different tea samples reached satisfactory values of 85.7-96.8%. Moreover, the adsorption of pesticides was spontaneous and followed Redlich-Peterson isotherm and pseudo-second-order kinetic models. These results demonstrate the sensitivity, effectiveness, and reliability of the proposed method for monitoring organochlorine and organophosphorus pesticides in tea samples, providing a preliminary basis for researchers to reasonably design adsorbents for the efficient extraction of pesticides., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The toxicity of organophosphorus pesticides (OPs) can catastrophically cause liver cell damage and inhibit the catalytic activity of cholinesterase. We designed and synthesized a near-infrared fluorescent probe HP-LZB with large Stokes shift which can specifically identify and detect butyrylcholinesterase (BChE) and visually explore the interaction between OPs and endogenous BChE in living cells. Fluorescence was turned on when HP-LZB was hydrolyzed into HP-LZ in the presence of BChE, and OPs could inhibit BChE's activity resulting in a decrease of fluorescence. Six OPs including three oxon pesticides (paraoxon, chlorpyrifos oxon and diazoxon) and their corresponding thion pesticides (parathion, chlorpyrifos and diazinon) were investigated. Both in vitro and cell experiments indicated that only oxon pesticides could inhibit BChE's activity. The limits of detection (LODs) of paraoxon, chlorpyrifos oxon and diazoxon were as low as 0.295, 0.007 and 0.011 ng mL -1 respectively and the recovery of OPs residue in vegetable samples was satisfactory. Thion pesticides themselves could hardly inhibit the activity of BChE and are only toxic when they are converted to their corresponding oxon form in the metabolic process. However, in this work, thion pesticides were found not be oxidized into their oxon forms in living HepG2 cells due to the lack of cytochrome P450 in hepatoma HepG2 cell lines. Therefore, this probe has great application potential in effectively monitoring OPs in real plant samples and visually exploring the interaction between OPs and BChE in living cells., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

For the first time, a magnetic carbon nanocomposite was synthesized using one-step hydrothermal procedure, employing bovine serum albumin, curcumin, and ferric ammonium citrate. Additionally, the application of this novel composite as an adsorbent for magnetic dispersive solid phase extraction of fungicides and pesticides from water and food samples is a unique aspect of this study. Under optimum conditions (salt concentration: 5.0% w/v, pH: 7.0, desorption solvent: ethanol, sorbent amount: 20 mg, extraction time: 20 min, desorption time: 3 min, stirring rate: 500 rpm, sample volume: 30 mL, extraction temperature: room temperature, and desorption solvent volume: 150 μL) linearity (2.5 to 1400 ng mL -1 ), coefficients of determination (R 2  ≥ 0.997), limits of detection (0.75 to 1.5 ng mL -1 ), and limits of quantification (2.5 to 5.0 ng mL -1 ) were achieved. The method validation results showed extraction recovery ranging from 71.2% to 93.4%, and preconcentration factors ranging from 142.5 to 186.1., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Phosphotriesterase (PTE) biodegradation of organophosphorus pesticides (OPs) is an efficient and environmentally friendly method. However, the instability and nonreusability of free PTE become the key factors restricting its practical application. In this study, a novel cross-linked magnetic hybrid nanoflower (CLMNF) was prepared. Molecular dynamics (MD) simulations were performed to further investigate the enhanced catalytic efficiency of the enzymes. The recovery rate of enzyme activity was 298% due to the large specific surface area and metal ion activation effect. More importantly, the immobilization scheme greatly improved the stability and reuse performance of the catalyst and simplified the recovery operation. CLMNFs retained 90.32% relative activity after 5 consecutive cycles and maintained 84.8% relative activity after 30 days at 25 °C. It has a good practical application prospect in the degradation and detection of OPs. Consequently, the immobilized enzyme as a biocatalyst has the characteristics of high efficiency, stability, safety, and easy separation, establishing the key step in a biodetoxification system to control organophosphorus contamination in food and the environment.

The residues of organophosphorus pesticides (OPs) are increasing environmental pollution and public health concerns. Thus, the development of simple, convenient and sensitive method for detection of OPs is crucial. Herein, a multifunctional Fe-based MOF with fluorescence, catalytic and adsorption, is synthesized by a simple one-pot hydrothermal method. The ratiometric fluorescence sensor for detection of OPs is constructed by using only one multifunctional sensing material. The NH 2 -MIL-101(Fe) is able catalyze the o-phenylenediamine (OPD) into 2,3-diaminophenazine (DAP) in the presence of H 2 O 2 . The generated DAP can significantly quench the intrinsic fluorescence of NH 2 -MIL-101(Fe) by the fluorescence resonance energy transfer (FRET) and internal filtration effect (IFE), while producing a new measurable fluorescence. Without immobilization or molecular imprinting, pyrophosphate ion (PPi) can inhibit the peroxidase-like activity of the NH 2 -MIL-101(Fe) by chelating with Fe 3+ /Fe 2+ redox couple. Moreover, PPi can also be hydrolyzed by alkaline phosphatase (ALP), the presence of OPs inhibits the activity of ALP, resulting in the increase of extra PPi preservation and signal changes of ratiometric fluorescence, the interactions of ALP with different OPs are explored by molecular docking, the OPs (e.g., glyphosate) interact with crucial amino acid residues (Asp, Ser, Ala, Lys and Arg) are indicated. The proposed sensor exhibits excellent detection performance for OPs with the detection limit of 18.7 nM, which provides a promising strategy for detection of OPs., Competing Interests: Declaration of competing interest The authors have no conflict of potential competing interest, financial or otherwise., (Copyright © 2024 Elsevier B.V. All rights reserved.)

pH plays an important role in the evaluation of the healthy status in versatile circumstances. The fluctuation of pH could be affected by complex internal and external stimuli. Especially, the abnormal pH changes is a common characteristic of organophosphorus pesticides (OPs)-caused damage owing to the irreversible inhibition of acetylcholinesterase (AChE) activity. Therefore, the rapid and efficient detection of pH changes is of great significance for predicting the OPs poisoning in living system. However, quick and convenient detecting pH levels in living cells is still limited by the lack of effective chemical tools. Here, a novel fluorescent probe TH-1 based on ESIPT mechanism was synthesized, showing specific fluorescent effects in different pH solutions. Importantly, the AChE catalyzed the hydrolysis product of acetylthiocholine iodide (ATCh) and changed the pH of solution, which influence its fluorescent intensity. Moreover, the probe TH-1 was applied to detecting the pH levels in living cells and C. elegans, providing an efficient chemical sensor for revealing the potential mechanisms of OPs in physiological and pathological processes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The current research aims to develop a new analytical method applying a dispersive liquid-liquid microextraction (DLLME) assisted by vortex and using an environmentally friendly extractant for the preconcentration of organochlorine and organophosphorus pesticides followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis. The extractant (i.e., natural deep eutectic solvent (NADES)) is safe, cheap, biodegradable and can be prepared by simply mixing DL-menthol and decanoic acid (molar ratio 2:1). The main experimental factors affecting the extraction of all analytes evaluated (19 organochlorine and organophosphorus pesticides) have been optimised using a multivariate analysis consisting in two steps: a Plackett-Burman design followed by a central composite design (CCD). Seven experimental factors have been evaluated: (i) sample volume; (ii) NADES volume; (iii) sample pH; (iv) extraction time; (v) centrifugation time; (vi) centrifugation speed; and (vii) ionic strength (NaCl %, w v -1 ). For the significant variables, the optimum values were 10 mL sample and 45 μL NADES. No pH adjustment as well as addition of NaCl were needed. The other variables were set at 3 min extraction time, 5 min centrifugation time and 900×g centrifugation speed, respectively. Under the optimised extraction conditions, the limit of quantification (LOQ) values ranged between 0.2 and 78 ng L -1 for all analysed pesticides. Furthermore, the proposed analytical method has been successfully applied to drinking water (bottled spring water). The recovery study (n = 3) has been evaluated at 0.1, 1.0 and 5.0 μg L -1 spiking levels, obtaining relative recovery values within the range of 70 % and 117 % and RSD values between 1 % and 20 % for all the analytes studied, except for p,p-DDT (56-77 % in high conductivity water samples)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Combined the electrostatic interaction of the negatively charged gold nanorods (AuNRs) (as acceptor) and Ru(bpy) 3 (as donor), an electrochemiluminescence resonance energy transfer (ECL-RET) sensor was constructed and applied for the detection of organophosphorus pesticides (OPs). Negatively charged AuNRs were synthesized by modifying AuNRs with polystyrene sulfonate (PSS) firstly, which can bind to Ru(bpy) 2+ (as donor), an electrochemiluminescence resonance energy transfer (ECL-RET) sensor was constructed and applied for the detection of organophosphorus pesticides (OPs). Negatively charged AuNRs were synthesized by modifying AuNRs with polystyrene sulfonate (PSS) firstly, which can bind to Ru(bpy) 3 2+ through electrostatic interaction so that the luminophore was absorbed by the acceptor, the resonance energy transfer occurred and only low ECL signal had been detected. Thiocholine can be produced by the hydrolysis process of acetylthiocholine (ATCh) with the help of acetylcholinesterase (AChE), which can bond with PSS-modified AuNRs (PSS-AuNRs) through gold-sulfur interaction, this caused the releasing of the adsorbed Ru(bpy) 3 2+ into the solution and resulting in the restoration of the ECL intensity. However, the activity of AChE was inhibited by OPs, and the recovery process of the ECL signal was thus suppressed as well. In this study, chlorpyrifos was chosen as model target, the results indicated that the correlation between the ECL intensity and the logarithm of chlorpyrifos concentration showed remarkable linearity across 1 ng/mL to 1 mg/mL, achieving a detection limit of 0.51 ng/mL. The proposed system has been utilized for detecting OPs in real samples with satisfied results., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Designing efficient and rapid methods for the detection of organophosphorus pesticides (OPs) residue is a prerequisite to mitigate their negative health impacts. In this study, we propose the concept of an enzyme catalysis system-based hydrogel kit integrated with a smartphone detector for in-field screening of OPs. Here, we rapidly prepared phosphotriesterase hybrid nanoflowers (PTE-HNFs) using a self-assembly strategy by adding external energy and embedded the nanocomposite in sodium alginate (SA) hydrogel to construct a target-responsive hydrogel kit. The color response of the kit is induced by catalyzing methyl parathion (MP) to produce p-nitrophenol. For on-site quantification, the color variations of the portable kit are converted into digital information through a smartphone, which exhibits an applicable linear range towards OPs. The hydrogel sensing platform demonstrates a wide linear range (1-150 μM) and low detection limit (0.15 μM) for MP while maintaining high reliability, excellent long-term stability, and ease of operation. Overall, the PTE-HNFs-based SA hydrogel kit provides a useful strategy for simple and sensitive detection of MP and holds great potential for applications in detecting OPs in food and environmental water., Competing Interests: Declaration of competing interest The authors declare that they have no conflicts of interest to this work., (Copyright © 2024 Elsevier B.V. All rights reserved.)

It is established that organophosphorus pesticide (OPP) toxicity results from modification of amino acids in active sites of target proteins. OPPs can also modify unrelated target proteins such as histones and such covalent histone modifications can alter DNA-binding properties and lead to aberrant gene expression. In the present study, we report on non-enzymatic covalent modifications of calf thymus histones adducted to selected OPPs and organophosphate flame retardants (OPFRs) in vitro using a bottom-up proteomics method approach. Histones were not found to form detectable adducts with the two tested OPFRs but were avidly modified by a few of the seven OPPs that were tested in vitro. Dimethyl phosphate (or diethyl phosphate) adducts were identified on Tyr, Lys and Ser residues. Most of the dialkyl phosphate adducts were identified on Tyr residues. Methyl and ethyl modified histones were also detected. Eleven amino residues in histones showed non-enzymatic covalent methylation by exposure of dichlorvos and malathion. Our bottom-up proteomics approach showing histone-OPP adduct formation warrants future studies on the underlying mechanism of chronic illness from exposure to OPPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2024. Published by Elsevier B.V. All rights reserved.)

In practical applications, the rapid and efficient detection of universal organophosphorus pesticides (OPs) can assist inspectors in quickly identifying the presence of OPs in samples. However, this presents a challenge for most well-established methods, typically designed to detect only a specific type of organophosphorus molecule at a time. In this proof-of-concept study, we draw inspiration from the structural similarities among OPs to develop innovative peptide-based fluorescence probes for the first time, which could efficiently detect a broad range of OPs within a mere 3 min. Analysis of fluorescence curve fitting reveals a clear linear correlation between the fluorescent intensity of the peptide probes and the concentration of OPs. Additionally, the selectivity analysis indicates that these peptide fluorescent probes exhibit an excellent response to various OPs while maintaining sufficient selectivity for detecting other pesticide types. Accurate sample analysis has also highlighted the potential of these peptide probes as practical tools for the rapid detection of OPs in actual vegetable samples. In summary, this proof-of-concept study presents an innovative approach to designing and developing ultrafast, universally peptide-based OP probes. These custom-designed peptide probes may facilitate rapid sample screening and offer initial quantification for OPs, potentially saving valuable time and effort in practical OP detection., Competing Interests: Declaration of competing interest The authors confirm that they do not have any known financial conflicts of interest or personal relationships that might have appeared to exert influence on the research presented in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

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 (R 2 ≥ 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.

Background: Organophosphorus pesticides (OPs) play important roles in the natural environment, agricultural fields, and biological prevention. The development of OPs detection has gradually become an effective strategy to avoid the dangers of pesticides abuse and solve the severe environmental and health problems in humans. Although conventional assays for OPs analysis such as the bulky instrument required analytical methods have been well-developed, it still remains the limitation of inconvenient, inefficient and lab-dependence analysis in real samples. Hence, there is an urgent demand to develop efficient detection methods for OPs analysis in real scenarios., Results: Here, by virtue of the highly efficient catalytic performance in Fe 7 S 8 nanoflakes (Fe 7 S 8 NFs), we propose an OPs detection method that rationally integrated Fe 7 S 8 NFs into the acetylcholine (ACh) triggered enzymatic cascade reaction (ATECR) for proceeding better detection performances. In this method, OPs serve as the enzyme inhibitors for inhibiting ATECR among ACh, acetylcholinesterase (AChE), and choline oxidase (CHO), then reduce the generation of H 2 O 2 to suppress the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) that catalyzed by Fe 7 S 8 NFs. Benefiting from the integration of Fe 7 S 8 NFs and ATECR, it enables a sensitive detection for OPs (e.g. dimethoate). The proposed method has presented good linear ranges of OPs detection ranging from 0.1 to 10 μg mL -1 . Compared to the other methods, the comparable limits of detection (LOD) of OPs are as low as 0.05 μg mL -1 ., Significance: Furthermore, the proposed method has also achieved a favorable visual detection performance of revealing OPs analysis in real samples. The visual signals of OPs can be transformed into RGB values and gathered by using smartphones, indicating the great potential in simple, sensitive, instrument-free and on-site analysis of pesticide residues in environmental monitoring and biosecurity research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: Organophosphorus pesticide (OP) exposure is known to have adverse effects on the nervous system. Children from agricultural communities are at risk of exposure to these chemicals from their indoor environments that can lead to neurological and developmental problems, including changes in behavior., Objective: The aim of this study is to evaluate whether the take-home pathway exposure is associated with behavioral and emotional problems in Latino Orchid Community children., Method: The study was implemented over a period of two years (2008-2010) in an orchard farming community with a total of 324 parents who had children between the ages of 5-12 years old. Mothers of the children were asked to complete the Child Behavior Checklist (CBCL) and dust from their carpets was collected. Emotional and behavioral deficits were assessed based on the CBCL and house dust was assessed for OP concentrations. In this study, correlations between OPs in house dust and CBCL subscales were estimated using linear regression models with total OP concentrations classified by tertiles. This study also facilitated the comparison between the agricultural and non-agricultural families in terms of behavioral deficits and house dust concentrations of pesticides., Results: The data from the study shows that there was a positive association between the concentration of OP residues in house dust and internalizing behavior (β=2.06, p=0.05) whereas the association with externalizing behavior was not significant after accounting for sociocultural covariates. Significant positive associations of OP residues with somatic problems (p=0.02) and thought problems (p=0.05) were also found., Conclusion: The data support a potential role of OP exposure in childhood development, with a specific focus on internalizing behavior. Future work focused on longitudinal studies may uncover the long-term consequences of OP exposure and behavior., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Diane Rohlman reports financial support was provided by National Institute for Occupational Safety and Health. Marie Gaine reports financial support was provided by University of Iowa Environmental Health Sciences Research Center. Khalid Khan reports financial support was provided by College of Health Sciences of Sam Houston State University. Diane Rohlman is currently an editor for Neurotoxicology Declaration of competing interests The authors have no conflicts of interest to declare., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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., (© 2024. The Author(s).)

The single-atom iron nanozyme (SA-Fe-NZ) exhibits high catalytic activity and excellent electron transfer efficiency in biosensors. However, the binding of bioreceptors to the surface of SA-Fe-NZ results in a decrease in the catalytic activity of the nanozyme due to its toxic effects. We utilized the toxic effects and excellent electrochemical properties of the SA-Fe-NZ to successfully construct a smartphone-assisted dual-mode biosensor. The complex formed by the binding of organophosphorus pesticides (OPs) to the aptamer exhibited toxic effects and inhibited the catalytic activity of the nanozyme, preventing the colorimetric substrate from being catalyzed. Simultaneously, the aptamers labeled with electrochemical signal molecules approached the electrode surface, causing a change in the electrochemical signal. The results demonstrated that the constructed broad-spectrum aptamer biosensor exhibited a low limit of detection of 3.55 fM and a wide linear range of 10 -13 -10 -2 M, allowing for qualitative and quantitative detection of multiple OPs in vegetables., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

A dual-mode sensor was developed for detecting acetylcholinesterase (AChE) and organophosphorus pesticides (OPs) via bifunctional BSA-CeO 2 nanoclusters (NCs) with oxidase-mimetic activity and fluorescence property. The dual-mode sensor has the characteristics of self-calibration and self-verification, meeting the needs of different detection conditions and provide more accurate results. The colorimetric sensor and fluorescence sensor have been successfully used for detecting AChE with limit of detection (LOD) of 0.081 mU/mL and 0.056 mU/mL, respectively, while the LOD for OPs were 0.9 ng/mL and 0.78 ng/mL, respectively. The recovery of AChE was 93.9-107.2% and of OPs was 95.8-105.0% in actual samples. A novel strategy was developed to monitor pesticide residues and detect AChE level, which will motivate future work to explore the potential applications of multifunctional nanozymes., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The ecological risks posed by widespread organophosphorus pesticide (OPs) pollution in the surface waters of China remain unclear. In this study, species sensitivity distribution (SSD) parametric statistical approaches were coupled with fully acute and chronic toxicity data to fit the sensitivity distributions of different aquatic species to five typical OPs: dimethoate, malathion, parathion-methyl, trichlorfon, and dichlorvos. Crustaceans exhibit the highest sensitivity to OPs, whereas algae are the least sensitive. The acute hazardous concentrations that affected 5 % of the species (HC 5 ) were 0.112, 0.001, 0.001, 0.001, and 0.001 mg/L for dimethoate, malathion, parathion-methyl, trichlorfon, and dichlorvos, respectively, whereas their chronic HC 5 values were 0.004, 0.004, 0.053, 0.001, and 0.0005 mg/L, respectively. Hence, dichlorvos is highly toxic and poses greater risk to non-target aquatic species. The evaluation data revealed varying geographical distribution characteristics of the ecological risks from OPs in 15 freshwater aquatic systems across different regions of China. Dichlorvos posed the highest risk in the basins of Zhejiang and Guangdong Provinces, with the highest chronic Risk Quotient (RQ) and Hazard Index (HI) at 9.34 and 9.92, respectively. This is much higher than what was collected and evaluated for foreign rivers (the highest chronic RQ and HI in foreign rivers were 1.65 and 2.24, respectively). Thus, dichlorvos in the surface waters of China poses a substantial ecological risk to aquatic organisms, and may endanger human health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Peroxidase (POD)-like can only function in acidic environments and the pH mismatch restricts the application of enzyme-nanozyme cascade catalytic sensing platforms in the broad-pH-responsive assay for organophosphorus pesticides (OPs). Herein, the metal-pyrimidine nanocubes (MPNCs) with intrinsic pH-switchable POD-like and catalase (CAT)-like properties were synthesized via the coordination of pyrimidin-2-ol with Cu 2+ . Meanwhile, acetylcholinesterase (AChE) and choline oxidase (CHO) were simultaneously encapsulated in MPNCs to construct an enzyme-nanozyme cascade catalytic platform (AChE/CHO@MPNCs). AChE/CHO@MPNCs could catalyze the hydrolysis of acetylcholine to choline, which was subsequently converted to H 2 O 2 . The POD-like activity of MPNCs was dominant under acidic conditions, while the CAT-like activity prevailed under neutral and alkaline conditions, which could catalyze H 2 O 2 to •OH and O 2 , respectively, then oxidizing dopamine (DA) to polydopamine quantum dots (PDA QDs) with different fluorescence characteristics. Consequently, OPs could be detected in a linear range from 0.05 to 1000 nM with a LOD of 0.015 nM in acidic environments and a linear range from 0.05 to 500 nM with a LOD of 0.023 nM in alkaline environments. Overall, our work expands the horizon of constructing enzyme@MOFs composites with high catalytic activity. Meanwhile, the intrinsic pH-switchable multienzyme-like property opens avenues to construct sensing platforms with broad-pH-responsive for OPs and other analytes detection., Competing Interests: Declaration of Competing Interest The authors declare that we have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Despite the serious health threats due to wide use of organophosphorus pesticides (OPPs) have been experimentally claimed to be remediated by probiotic microorganisms in various food and organism models, the interactions between OPPs and probiotics in the natural wetland ecosystem was rarely investigated. This study delves into the spatial and temporal distribution, contamination levels of OPPs in the Baiyangdian region, the diversity of probiotic communities in varying environmental contexts, and the potential connection with OPPs on these probiotics. In typical shallow lake wetland ecosystem-Baiyangdian lake in north China, eight OPPs were identified in the lake sediments, even though their detection rates were generally low. Malathion exhibited the highest average content among these pesticides (9.51 ng/g), followed by fenitrothion (6.70 ng/g). Conversely, chlorpyrifos had the lowest detection rate at only 2.14%. The region near Nanliu Zhuang (F10), significantly influenced by human activities, displayed the highest concentration of total OPPs (136.82 ng/g). A total of 145 probiotic species spanning 78 genera were identified in Baiyangdian sediments. Our analysis underscores the relations of environmental factors such as phosphatase activity, pH, and electrical conductivity (EC) with probiotic community. Notably, several high-abundance probiotics including Pseudomonas chlororaphis, Clostridium sp., Lactobacillus fermentum, and Pseudomonas putida, etc., which were reported to exhibit significant potential for the degradation of OPPs, showed strongly correlations with OPPs in the Baiyangdian lake sediments. The outcomes of this research offer valuable insights into the spatiotemporal dynamics of OPPs in natural large lake wetland and the probability of their in-situ residue bioremediation through the phosphatase pathway mediated by probiotic such as Lactic acid bacteria in soils/sediments contaminated with OPPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Ethephon (ETH), a commonly employed growth regulator, poses potential health risks due to its residue in fruits and vegetables, leading to both acute and subchronic toxicity. However, the detection accuracy of ETH is compromised by the color effects of the samples during the detection process. In this work, a multienzyme reaction-mediated electrochemical biosensor (MRMEC) was developed for the sensitive, rapid, and color-interference-resistant determination of ETH. Nanozymes Fe 3 O 4 @Au-Pt and graphene nanocomplexes (GN-Au NPs) were prepared as catalysts and signal amplifiers for MRMEC. Acetylcholinesterase (AChE), acetylcholine (ACh), and choline oxidase (CHOx) form a cascade enzyme reaction to produce H 2 O 2 in an electrolytic cell. Fe 3 O 4 @Au-Pt has excellent peroxidase-like activity and can catalyze the oxidation of 3,3',5,5'-tetramethvlbenzidine (TMB) in the presence of H 2 O 2 , resulting in a decrease in the characteristic peak current of TMB. Based on the inhibitory effect of ETH on AChE, the differential pulse voltammetry (DPV) current signal of TMB was used to detect ETH, offering the limit of detection (LOD) of 2.01 nmol L -1 . The MRMEC method effectively analyzed ETH levels in mangoes, showing satisfactory precision (coefficient of variations, 2.88-15.97%) and recovery rate (92.18-110.72%). This biosensor holds promise for detecting various organophosphorus pesticides in food samples.

Organophosphorus pesticides (OPs) are of great concern due to its potential harms on human health and the environment. Herein, a budget-friendly, rapid and convenient colorimetric sensing platform is developed for detection of OPs in the environmental and food samples. The sensing element, PANI-MnO 2 nanozyme with excellent oxidase mimetic activity is synthesized at room temperature, which is able to directly oxidize 3,3,5,5-tetramethylbenzidine (TMB) to generate blue colored oxidized TMB (OxTMB) within 2 min. Ascorbic acid (AA) can inhibit the oxidization reaction of TMB, consequently causing the blue color fading. Ascorbic acid 2-phosphate (AAP) could be hydrolyzed to produce AA by alkaline phosphatase (ALP). In the presence of OPs can effectively decrease ALP activity, resulting in the recovery of catalytic activity of PANI-MnO 2 . Therefore, sensitive and selective OPs detection is achieved. Under the optimal conditions, excellent detection performance in term of glyphosate as a model is achieved with a linear range from 0.50 to 50 μM, the detection limit is 0.39 μM (S/N = 3). The utility of method is further improved by combining a portable smartphone platform with a color picking application. The colorimetric platform achieves instrument-free detection of OPs and overcomes the uneven color distribution of traditional paper-based chip, providing an alternative strategy for the qualitative discernment and semi-quantitative analysis of OPs on-site., Competing Interests: Declaration of competing interest The authors declare no potential competing interests in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Organophosphorus pesticides (OPPs) are a group of neurotoxic compounds that can cause neural dysfunction, overstimulation, paralysis, and even death to numerous non-target organisms. Despite their potential ecological impacts, there is a lack of research on water quality criteria (WQC) for OPPs, which hinders the risk assessment for these pollutants. This study aimed to derive short-term and long-term water quality criteria (SWQC and LWQC, respectively) for eight common OPPs through the species sensitivity distribution (SSD) methodology. The ecological risk of these compounds in aquatic environments was consequently assessed using a four-level tiered approach. The results showed that the derived SWQC ranged from 0.0245 μg/L (chlorpyrifos) to 18.6 μg/L (dimethoate), while the LWQC ranged from 0.326 ng/L (chlorpyrifos) to 0.354 μg/L (dimethoate). OPPs were widely recorded in different waters with concentrations up to 40.9 μg/L. The tiered approach results indicated that most OPPs had a low acute risk but a severe chronic risk. The estimated chronic hazard quotients (HQ) were calculated with a maximum of 4782, the exceedance probabilities with a maximum of 97.6%, and the overall probabilities (ORP) with a range of between 0.08% and 11.5%. These findings suggest that the contamination of OPPs in aquatic environments warrants further concern., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Most of covalent organic frameworks (COFs) are non or weakly emissive due to either the molecular thermal motion-mediated energy dissipation or the aggregation-caused quenching (ACQ) effect. Herein, we synthesize an imine-linked COF (TFPPy-TPh-COF) with high electrochemiluminescence (ECL) emission and the capability of eliminating the ACQ effect and further construct an ECL sensor for malathion detection. The imine-linked COF is obtained by the condensation reaction of (1,1':3',1″-terphenyl)-4,4″-diamine (TPh) and 1,3,6,8-tetrakis(p-formylphenyl)pyrene (TFPPy), and it has higher ECL efficiency than TFPPy aggregates due to the separation of ACQ luminophores (i.e., TFPPy) from each other by TPh and the restriction of intramolecular motions of TFPPy and TPh to reduce the nonradiative decay. The efficient quenching of ECL is achieved by electrochemiluminescence resonance energy transfer (ERET) from the excited state of the TFPPy-TPh-COF to zeolite imidazolate framework-8 (ZIF-8) and the steric hindrance of ZIF-8. Acetylcholinesterase (AChE) can enzymatically hydrolyze acetylcholine (ACh) to generate acetic acid. The resultant acetic acid can trigger the dissolution of ZIF-8 to produce an enhanced ECL signal. Malathion as an organophosphorus pesticide serves as an AChE inhibitor to prevent the production of acetic acid, inducing the decrease of ECL signal. This sensor displays a limit of detection (LOD) of 2.44 pg/mL and a wide dynamic detection range of 0.01-1000 ng/mL. Furthermore, it can be used to detect other organophosphates pesticides (e.g., methidathion, chlorpyrifos, and paraoxon) and measure malathion in real samples (i.e., pakchoi, lettuce, and apples)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Organophosphorus pesticides (OPPs) and organophosphate esters (OPEs) are organophosphorus compounds created as substitutes for persistent environmental pollutants, namely organochlorines pesticides and brominated flame retardants, respectively. However, there is evidence that organophosphorus compounds are also widespread across the environment and have adverse effects on biota. In humans, OPPs and OPEs were reported to be carcinogenic, neurotoxic, hepatotoxic, nephrotoxic, amongst others. As lipophilic compounds, these accumulate in fat tissues as adipose tissue. Yet biomonitoring studies and analytical methodologies to assess these compounds in the human body are scarce, particularly in adipose tissue. In this study, the presence of six OPPs and seven OPEs was determined in samples of subcutaneous adipose tissue (scAT) and visceral adipose tissue (vAT) from 188 adult obese women. OPPs and OPEs were quantified by gas chromatography (GC) flame photometric detection and confirmed in GC tandem mass spectrometry. The detection frequencies ranged between 0.5-1.6% and 48-53%, respectively for OPPs and OPEs. Organophosphorus pollutants were present in both adipose tissues and median concentrations were 0.008 ± 0.020 μg/g scAT and 0.009 ± 0.020 μg/g vAT. A total of 32 Spearman's correlations were found between organophosphorus pollutants concentrations in adipose tissue and several biochemical parameters (18 positive and 14 negative). Our results show that anthropometric and hormonal parameters, cholesterol, glycaemia, macrominerals, urea and sedimentation velocity might be influenced by the presence of these compounds. The presence of organophosphorus pollutants in the environmental and their possible effect on female metabolic processes is concerning. Particularly because presently OPEs usage is not controlled or limited by any regulation. More studies are needed to fully understand these pollutants behaviour and hazard effects on human health, biota, and the environment so control regulations can be drawn to prevent and lessen their effects., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

In view of the potential hazards of organophosphorus pesticides (OPs), this paper constructed a ratiometric fluorescent probe utilizing a functionalized metal-organic framework to detect OPs. Ru(bpy) 3 Cl 2 was encapsulated inside UiO-66 as a reference signal, and MnO 2 nanosheets (MnO 2 NSs) were grown on the surface to obtain Ru@UiO-66@MnO 2 NSs. Acetylcholinesterase catalyzed the decomposition of acetylcholine into reductive thiocholine, which consumed MnO 2 NSs, thus restoring the Ru@UiO-66 fluorescence. Due to the enzymatic inhibition of OPs and the redox reaction between MnO 2 NSs and thiamine, this probe emitted blue fluorescence in the presence of OPs. The probe achieved linear responses to dichlorvos and chlorpyrifos with LODs of 9.99 × 10 -6 μg mL -1 and 9.99 × 10 -5 μg mL -1 . The probe exhibited a satisfactory recovery rate for OPs in green tea. Furthermore, a hydrogel detection platform was developed by embedding the probe into sodium alginate. Overall, this work provides a visual approach to detect OPs in agricultural products., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Organophosphorus pesticides (OPs) are widely used in agricultural production, but their residues could cause pollution to the environment and living organisms. In this paper, a simple dual-readout method for OPs detection was proposed based on ChOx single enzyme inhibition. Firstly, ChOx can catalyze the production of H 2 O 2 from choline chloride (Ch-Cl). Bifunctional iron-doped carbon dots (Fe-CDs) with good peroxidase-like activity and superior fluorescence properties can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB (oxTMB) by H 2 O 2 formed, and oxTMB could quench the fluorescence of Fe-CDs. In light of the fact that OPs exhibited activity in inhibiting ChOx, less H 2 O 2 and the decreasing oxTMB led to a result that the fluorescence of the system recovered and the solution became lighter in blue color. Moreover, the process of ChOx inhibition by OPs was analyzed by molecular docking technique and it was found that OPs interact with key amino acid residues catalyzed by ChOx (Asn510, His466, Ser101, His351, Phe357, Trp331, Glu312). Finally, a dual-mode (colorimetry and fluorescence) sensor was created for the detection of OPs with the detection limit of 6 ng/L, and was successfully used in the quantitative determination of OPs in actual samples with satisfactory results., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The residues of pesticides and antibiotics have always been a major concern in agriculture and food safety. In order to provide a new method for the rapid detection of organophosphorus pesticides and antibiotics, a novel Cd(II) chain-based zwitterionic metal-organic framework MOF 1 with high sensitivity fluorescence sensing performance was successfully synthesized. A series of researches showed that the water- and pH-stable bifunctional MOF 1 has a great ability to detect phosmet (PSM) and chlortetracycline (CTC) in water through fluorescence quenching effect, with high detection sensitivity, low detection limits (0.0124 μM and 0.0131 μM), short response time (40 s) and reusability. Practical application results revealed that MOF 1 could detect PSM and CTC in milk, beef, chicken and egg samples, with satisfactory recoveries (95.2%-103.7%). As a novel fluorescence probe, MOF 1, is known the first case that can detect PSM in animal-derived samples, and the first dual-function material capable of detecting PSM and CTC. Mechanism studies displayed that competitive absorption and photoinduced electron transfer clearly authenticate the high quenching performance of the material., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this work, different sol-gel sorbent-coated second-generation fabric phase sorptive extraction (FPSE) membranes were synthesized using titania-based sol-gel precursors. The proposed membranes were tested for their efficiency to extract eleven selected organophosphorus pesticides (OPPs) from apple juice samples. Among the examined materials, sol-gel C 18 coated titania-based FPSE membranes showed the highest extraction efficiency. These membranes were used for the optimization and validation of an FPSE method prior to analysis by gas chromatography-mass spectrometry. The detection limits for OPPs ranged between 0.03 and 0.08 ng mL -1 . Moreover, the relative standard deviation was < 8.2% and 8.4% for intra-day and inter-day studies, respectively. The relative recoveries were 91-110% (intra-day study) and 90-106% (inter-day study) for all the target analytes, demonstrating good overall method accuracy. Moreover, the novel membranes were reusable at least 5 times. The titania-based membranes were compared to the conventional silica-based membranes and their utilization resulted in higher extraction recoveries., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Accurate pesticide identification is of great importance for regulating food safety. However, the discrimination between organophosphorus pesticides (OPs) and carbamate pesticides (CPs) is still a challenge for existing analytical methods based on cholinesterase inhibition. It mainly because of the similar inhibitory effect of OPs and CPs on cholinesterase. Herein, we found that OPs and CPs differentially affected nanozymes with laccase-like activity, which would be interfered by OPs in different degrees rather than CPs. Thus, we fabricated a nanozyme sensor array and successfully achieved the OPs identification and similar individual discrimination, ignoring the interference from CPs or other potential interferents (antibiotics, ions, other pesticides). On the basis of nanozyme sensor array, a portable method using smartphone was constructed and utilized to determine OPs in fruits and vegetables. This work would contribute to the development of portable sensors and the highly selective identification and discrimination of OPs in complex samples., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Organophosphorus pesticide (OP) residues pose a serious threat to human health, motivating the search for novel adsorbents and detection methods. Herein, defective copper-based metal organic frameworks (Cu-MOFs) were synthesized by the reaction of Cu 2+ ions and 1,3,5-benzenetricarboxylate linkers in the presence of acetic acid. As the amount of acetic acid increased, the crystallization kinetics and morphology of the Cu-MOFs changed, leading to mesoporous Cu-MOFs with many large surface pores (defects). Adsorption studies of OPs revealed the defective Cu-MOFs showed faster pesticide adsorption kinetics and higher pesticide adsorption capacities. Density functional theory calculations showed that pesticide adsorption in the Cu-MOFs was mainly electrostatic. A dispersive solid phase extraction method was developed based on a defective Cu-MOF-6 for rapidly extracting pesticides from food samples. The method allowed pesticide detection over a wide linear concentration range, low limits of detection (0.0067-0.0164 µg L -1 ) and good recoveries in pesticide-spiked samples (81.03-109.55%)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Emerging contaminants (ECs) are commonly found in environmental media. Yet leachate from municipal solid waste incineration plants (MSWIPs), which can serve as a reservoir for various contaminants, including ECs, has received little investigation. To address this gap, 65 ECs were analyzed in the fresh leachate and biological effluent from three major MSWIPs in Shanghai. Results indicated that over half (56%) of the 65 ECs were detected in fresh leachate. Different ECs would be removed to varying degrees after biological treatment, including polycyclic aromatic hydrocarbons (PAHs) (65%), polybrominated diphenyl ethers (PBDEs) (51%), phthalate esters (PAEs) (36%), and organophosphorus pesticides (OPPs) (34%). Notably, for tetrabromobisphenol A (TBBPA), a PBDE substitute, only 2% was removed after biological treatment, while polychlorinated biphenyls (PCBs) were effectively removed at 83%. Water solubility and the octanol-water partition coefficient are key factors influencing the distribution and removal of ECs in leachate. the effluent will still contain refractory ECs even after the biological treatment. These residual ECs discharged to sewers can impact wastewater treatment plants or contaminate surface water and groundwater. These findings provide insights into the leachate contamination by ECs, their environmental fate, factors affecting their behavior, and potential environmental impacts., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Design and preparation of new fiber coatings for solid-phase microextraction (SPME) is of significance to the sample preparation techniques. Herein, a facile strategy has been developed for the integration of the black phosphorus (BP) nanosheets with metal-organic framework (ZIF-8) to generate a BP/ZIF-8 nanocomposite. For the first time, the newly-synthesized BP/ZIF-8 nanocomposite was adopted as the SPME fiber coating for the extraction of organophosphorus pesticides (OPPs). Under the optimized conditions, the BP/ZIF-8 based SPME method gained acceptable linearity (0.04-20 µg L -1 ), low limits of detection (0.012-0.051 µg L -1 ) and good repeatability (3.2-8.1%). Coupled with gas chromatography-mass spectrometric detection, the developed SPME method was successfully used for the preconcentration of OPPs from environmental waters with the method recoveries from 92.0%-103.8%. This method offers a good alternative for the analysis of trace OPPs in environmental water samples., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this work, metal-organic frameworks (MOFs) including Fe-MIL-101 and Ti-MIL-125 were prepared and fixed on the melamine foam (MF) by polyvinylidene fluoride (PVDF) to prepare MF/PVDF/MOFs, which was used as adsorbents in pipette-tip solid-phase extraction (PT-SPE) for rapid extraction of organophosphorus pesticides (OPPs). Then, a gas chromatograph-flame thermionic detector (GC-FTD) was used for simultaneous analysis of Dimethoate (DMT), Iprobenfos (IBF), Parathion-methyl (PAM), and Chlorpyrifos (CPF). The morphology, crystal structure, and functional groups of MF/PVDF/MOFs were characterized, indicating that Ti-MIL-125 and Fe-MIL-101 were successfully synthesized and distributed on MF. The Fe-MIL-101 and Ti-MIL-125 showed good extraction ability for OPPs, which was mainly due to the π-π interaction and the multiple porous structures. Under the optimal conditions, the limit of detection (LODs) of four OPPs was 0.03-0.14 μg L -1 and the RSDs were less than 9.9%. The developed PT-SPE method showed a short extraction time (<3 min). The recoveries in fruits and vegetables (Celery, cabbages, and oranges) ranged from 75.3%-118.8% (RSDs<9.6%). The prepared MF/PVDF/MOFs demonstrated the efficient extraction performance of OPPs, contributing to the rapid pretreatment of OPPs from food and the environment., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Organophosphorus pesticides (OPPs) are widely used in agricultural production due to their chemical stability, high efficiency and low cost. It should be emphasized that OPPs can seriously harm aquatic organisms after entering the water environment through leaching and other ways. To this end, this review combines a new method to quantitatively visualize and summarize information on developments in this field to review the latest progress in OPPs toxicity, propose scientific trends and research hotspots. Among all countries, China and the United States have published a large number of articles and played a leading role. Based on the detection of co-occurrence keywords, it is emphasized that "OPPs cause oxidative stress in organisms", which reflects that the main factor of OPPs toxicity is the occurrence of oxidative stress. Researchers also focused on studies involving AchE activity, acute toxicity and mixed toxicity. This reveals that OPPs mainly affect the nervous system, and higher organisms are more resistant to the toxic effects of OPPs than lower organisms due to their strong metabolic capacity. As for the mixed toxicity of OPPs, most OPPs have synergistic toxic effects. Moreover, the analysis of keyword bursts revealed that the study of OPPs on the immune response of aquatic organisms and the effect of temperature on toxicity will become new research trends. In conclusion, this scientometric analysis can provide a scientific basis for improving the aquatic ecological environment and rationally using OPPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Objective: The epidemiological evidence of human exposure to organophosphorus pesticides (OPPs) with type 2 diabetes mellitus (T2DM) and prediabetes (PDM) is scarce. We aimed to examine the association of T2DM/PDM risk with single OPP exposure and multi-OPP co-exposure., Methods: Plasma levels of ten OPPs were measured using the gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) among 2734 subjects from the Henan Rural Cohort Study. We used generalized linear regression to estimate odds ratios (ORs) or β with 95% confidence intervals (CIs), and constructed quantile g-computation and Bayesian kernel machine regression (BKMR) models to investigate the association of OPPs mixture with the risk of T2DM and PDM., Results: High detection rates ranged from 76.35% (isazophos) to 99.17% (malathion and methidathion) for all OPPs. Several plasma OPPs concentrations were in positive correlation with T2DM and PDM. Additionally, positive associations of several OPPs with fasting plasma glucose (FPG) values and glycosylated hemoglobin (HbA1c) levels were observed. In the quantile g-computation, we identified significantly positive associations between OPPs mixtures and T2DM as well as PDM, and fenthion had the greatest contribution for T2DM, followed by fenitrothion and cadusafos. As for PDM, the increased risk was largely explained by cadusafos, fenthion, and malathion. Furthermore, BKMR models suggested that co-exposure to OPPs was linked to an increased risk of T2DM and PDM., Conclusion: Our findings suggested that the individual and mixture of OPPs exposure were associated with an increased risk of T2DM and PDM, implying that OPPs might act an important role in the development of T2DM., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

A biosafe magnetic Fe 3 O 4 @SiO 2 @Salg (GMS) was successfully developed via a simple and economic method. Fe 3 O 4 @SiO 2 particles were selected as the magnetic core, and they directly interacted with sodium alginate, thus mitigating the use of cross-linking agents. The microstructure, properties, and formation mechanism of GMS were examined using FE-SEM, TEM, VSM, TGA, zeta potential, and FT-IR. The as-developed GMS was used as a desirable adsorbent to remove organophosphorus pesticides (OPPs) from water bodies, and the influence of different factors on the removal efficiencies of OPPs was investigated. Optimal preparation conditions were determined, and the excellent removal efficiencies of the 18 OPPs were achieved in this study (80.5%-100% for tap, river, and seawater). After the GMS was recycled eight times, the removal efficiencies of 18 OPPs were maintained at >80%. Adsorption kinetics and isotherm models showed that the adsorption process was accurately fitted with the Langmuir isotherm and pseudo-second-order models. The values of ΔG, ΔH, and ΔS were negative, indicating that the OPPs were adsorbed on the GMS spontaneously via an exothermal reaction, and chemisorption was the dominant adsorption mechanism. Overall, the as-developed GMS was biosafe as revealed by cytotoxicity experiments. GMS had good environmental security, stability, and reusability, and it exhibited excellent potential for removing OPPs from aqueous solutions without causing secondary pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Freshwater planarian are emerging as a valuable in vivo model for (eco) toxicological studies, but the lack of harmonization of procedures between laboratories remains a challenge. This study aimed to optimize, automate and select the best behavioural tests and analyse the potential of different planarian species as models for toxicological assessment. We implemented four tests: exploration, photomotor response, Tapping and Planarian Light Dark Test, on different planaria species using the DanioVision system. We conclude that the exploration assay performed in 24 well-plate at 10,000 lux is the one that is robust and reliable for toxicological studies with planaria. Dugesia japonica and Schmidtea mediterranea have proved to be sensitive models for toxicological screening of organophosphorus pesticides through behavioural analysis. Under necessary experimental conditions, the motility baseline in controls, for both species allowed the detection of behavioural changes, making both good models for behavioural testing in (eco) toxicological context., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Pesticide residues significantly affect food safety and harm human health. In this work, a series of near-infrared fluorescent probes were designed and developed by acylating the hydroxyl group of the hemicyanine skeleton with a quenching moiety for monitoring the presence of organophosphorus pesticides in food and live cells. The carboxylic ester bond on the probe was hydrolyzed catalytically in the presence of carboxylesterase and thereby the fluorophore was released with near-infrared emission. Notably, the proposed probe 1 exhibited excellent sensitivity against organophosphorus based on the carboxylesterase inhibition mechanism and the detection limit for isocarbophos achieved 0.1734 μg/L in the fresh vegetable sample. More importantly, probe 1 allowed for situ visualization of organophosphorus in live cells and bacteria, meaning great potential for tracking the organophosphorus in biological systems. Consequently, this study presents a promising strategy for tracking pesticide residues in food and biological systems., (© 2023. Springer-Verlag GmbH Germany, part of Springer Nature.)

A fast, eco-friendly and accurate ratiometric fluorescent strategy is presented for the determination of organophosphorus pesticides (OPs) using intrinsic dual-emission silica nanoparticles modified with Rhodamine 6G (SiNPs-Rho6G). SiNPs-Rho6G had intrinsic dual-emission at 410 and 550 nm. The substrate acetylcholine was catalyzed by acetylcholinesterase (AChE) to produce thiocholine (TCh). TCh triggered the specific reaction of Ellman's reagent 5, 5-dithiobis (2-nitrobenzoic acid) to obtain 5-thio-2-nitrobenzoic acid, which caused the decrease in fluorescence intensity of SiNPs-Rho6G at 410 nm by the inner filter effect, while the fluorescence intensity of SiNPs-Rho6G at 550 nm was not significantly changed. OPs caused the recovery of the fluorescence at 410 nm by inhibiting the activity of AChE. Thus, the quantitative detection of OPs could be achieved through utilizing the catalytic characteristic of AChE. The linear curve from 0.010 to 0.250 μg mL -1 with a detection limit of 7 ng mL -1 was obtained for the determination of chlorpyrifos (Cpf). The ratiometric probe was used to detect the spiked Cpf in environmental and food samples with good recoveries. Therefore, combined with the dual emission characteristics of SiNPs-Rho6G and the specificity of the enzyme, the ratio fluorescence sensing platform has potential application prospects in OPs determinations., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Organophosphorus pesticides such as glyphosate and glufosinate are used worldwide, and environmental regulatory values are being adopted in many countries due to their potential toxicity. In the present work, a pretreatment-free analytical method is established in which these two compounds with their metabolites are isolated from each other by anion-exchange HPLC using ammonium acetate (70 mM, pH 3.7) as eluent, and they are detected by triple quadrupole ICP-MS. Very low detection limits of 0.03-0.17 μg L -1 are acquired through the detection of P + as PO + via oxygen reaction mode, and quantitative recovery was obtained from the spike-recovery test on river water samples containing phosphate ion as an isobaric interferent. In addition, a constant sensitivity per molar concentration was achieved regardless of the compounds due to the powerful ion source of ICP-MS. This property suggests that semi-quantitative analysis of unknown P-bearing compounds is possible from one calibration curve., (© 2023. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

The abuse of organophosphorus pesticides (OPPs) in tea planting makes it easy to transfer from tea into its infusion, bringing potential health risks to consumers. Thus, it is essential to adopt reliable techniques to remove OPPs from tea infusion. In this study, three treatment methods were used to modify carbonized bacterial cellulose (CBC) to improve its adsorption performance. Among them, CBC treated by hydrazine hydrate (N-CBC) had the best adsorption effect, whose removal rate for dicrotophos is 13 times that of CBC. The in-depth study of adsorption mechanism proved that hydrophobic interaction dominated the adsorption of OPPs onto N-CBC. The pseudo-second-order kinetic model and Langmuir isotherm model were more suitable to describe the process. Additionally, there were no significant changes in tea infusion quality after N-CBC treatment. This work clarifies that N-CBC benefitted from simple preparation method, excellent adsorption performance and unique adsorption mechanism has potential applications in tea infusion., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Engineering efficient dual-mode portable sensor with built-in cross reference correction is of great significance for onsite reliable and precise detection of organophosphorus pesticides (OPs) and evading the false-positive outputs, especially in emergency case. Currently, most nanozyme-based sensors for OPs monitoring primarily replied on the peroxidase-like activity, which involved unstable and toxic H 2 O 2 . In this scenario, a hybrid oxidase-like 2D fluorescence nanozyme (PtPdNPs@g-C 3 N 4 ) was yielded by in situ growing PtPdNPs in the ultrathin two-dimensional (2D) graphitic carbon nitride (g-C 3 N 4 ) nanosheet. When acetylcholinesterase (AChE) hydrolyzed acetylthiocholine (ATCh) to thiocholine (TCh), it ablated O 2 - • from the dissolved O 2 catalyzed by PtPdNPs@g-C 3 N 4 's oxidase-like activity, hampering the oxidation of o-phenylenediamine (OPD) into 2,3-diaminophenothiazine (DAP). Consequently, with the increasing concentration of OPs which inhibited the blocking effect by inactivating AChE, the produced DAP caused an apparent color change and a dual-color ratiometric fluorescence change in the response system. Through integrating into a smartphone, a H 2 O 2 -free 2D nanozyme-based onsite colorimetric and fluorescence dual-mode visual imaging sensor for OPs was proposed with acceptable results in real samples, which holds vast promise for further development of commercial point-of-care testing platform in early warning and controlling of OPs pollution for safeguarding environmental health and food safety., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The determination of organophosphorus pesticides in urine is useful for evaluating human exposure. In this study, a simple micro-solid-phase extraction method based on a polydopamine-modified monolithic spin column combined with liquid chromatography-mass spectrometry (LC-MS) was developed for the determination of six organophosphorus pesticides (dimethoate, dichlorvos, carbofuran, methidathion, phosalone, and chlorpyrifos) in urine samples. A methacrylate polymer monolithic support was prepared in situ in the spin column, and dopamine solution was repeatedly passed through the monolith matrix via centrifugation to generate a polydopamine layer in the polymeric network. All extraction steps were performed via centrifugation. The monolith exhibited good permeability, which enabled high-flow-rate sample loading and significantly reduced the sample pre-treatment time. The addition of polydopamine significantly improved the extraction efficiency of the monolithic spin column owing to the catechol and amine groups in dopamine, which can enhance hydrogen bonding and π-π stacking. Factors affecting the extraction, including the solution pH, centrifugation speed, and desorption solvent, were investigated to determine the optimal extraction conditions. Under the optimal conditions, the OPP detection limits were 0.02-1.32 µg/L. The relative standard deviations of the single column (n = 5) and column-to-column (n = 3) precision for the extraction method were <11%. The monolithic spin column exhibited high stability and could be used for more than 40 extraction cycles. The recoveries for spiked urine samples were 72.1-109.3% (RSDs: 1.6-7.9%). The developed method was successfully applied to the simple and rapid analysis of organophosphorus pesticides in urine samples., Competing Interests: Declaration of Competing Interest The authors have declared no conflict of interest., (Copyright © 2023. Published by Elsevier B.V.)

It is still challenging to achieve simultaneous and sensitive detection of multiple organophosphorus pesticides (OPs). Herein, we optimized the ssDNA templates for the synthesis of silver nanoclusters (Ag NCs). For the first time, we found that the fluorescence intensity of T base-extended DNA-templated Ag NCs was over three times higher than the original C-riched DNA-templated Ag NCs. Moreover, a "turn-off" fluorescence sensor based on the brightest DNA-Ag NCs was constructed for the sensitive detection of dimethoate, ethion and phorate. Under strong alkaline conditions, the P-S bonds in three pesticides were broken, and the corresponding hydrolysates were obtained. The sulfhydryl groups in the hydrolyzed products formed Ag-S bonds with the silver atoms on the surface of Ag NCs, which resulted in the aggregation of Ag NCs, following the fluorescence quenching. The fluorescence sensor showed that the linear ranges were 0.1-4 ng/mL for dimethoate with a limit of detection (LOD) of 0.05 ng/mL, 0.3-2 µg/mL for ethion with a LOD of 30 ng/mL, and 0.03-0.25 µg/mL for phorate with a LOD of 3 ng/mL. Moreover, the developed method was successfully applied to the detection of dimethoate, ethion and phorate in lake water samples, indicating a potential application in OP detection.