Universal organophosphate pesticides detection by peptide based fluorescent probes.

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.

Ambient long-term exposure to organophosphorus pesticides and the human gut microbiome: an observational study.

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.

Potential Common Mechanisms of Cytotoxicity Induced by Organophosphorus Pesticides via NLRP3 Inflammasome Activation.

The Multi-Threat Medical Countermeasure (MTMC) technique is crucial for developing common biochemical signaling pathways, molecular mediators, and cellular processes. This study revealed that the Nod-like receptor 3 (NLRP3) inflammasome pathway may be a significant contributor to the cytotoxicity induced by various organophosphorus pesticides (OPPs). The study demonstrated that exposure to six different types of OPPs (paraoxon, dichlorvos, fenthion, dipterex, dibrom, and dimethoate) led to significant cytotoxicity in BV2 cells, which was accompanied by increased expression of NLRP3 inflammasome complexes (NLRP3, ASC, Caspase-1) and downstream inflammatory cytokines (IL-1ß, IL-18), in which the order of cytotoxicity was dichlorvos > dipterex > dibrom > paraoxon > fenthion > dimethoate, based on the IC50 values of 274, 410, 551, 585, 2,158, and 1,527,566 µM, respectively. The findings suggest that targeting the NLRP3 inflammasome pathway could be a potential approach for developing broad-spectrum antitoxic drugs to combat multi-OPPs-induced toxicity. Moreover, inhibition of NLRP3 efficiently protected the cells against cytotoxicity induced by these six OPPs, and the expression of NLRP3, ASC, Caspase-1, IL-1ß, and IL-18 decreased accordingly. The order of NLRP3 affinity for OPPs was dimethoate > paraoxon > dichlorvos > dibrom > (fenthion and dipterex) based on K D values of 89.8, 325, 1,460, and 2,690 µM, respectively. Furthermore, the common molecular mechanism of NLRP3-OPPs was clarified by the presence of toxicity effector groups (benzene ring, nitrogen/oxygen-containing functional group); =O, -O-, or =S (active) groups; and combination residues (Gly271, Asp272). This finding provided valuable insights into exploring the common mechanisms of multiple threats and developing effective therapeutic strategies to prevent OPPs poisoning.

Smartphone-assisted hydrogel platform based on BSA-CeO2 nanoclusters for dual-mode determination of acetylcholinesterase and organophosphorus pesticides.

A dual-mode sensor was developed for detecting acetylcholinesterase (AChE) and organophosphorus pesticides (OPs) via bifunctional BSA-CeO2 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.

In vitro effect of diazoxon on cell signaling and second messengers in Nile tilapia (Oreochromis niloticus) leukocytes.

The physiological and molecular responses of leukocytes are altered by organophosphate pesticides (OPs). Some reports have shown that diazinon (DZN) causes immunotoxic effects; diazoxon (DZO), the oxon metabolite of DZN, is attributed to influence the immune response by affecting the leukocyte cholinergic system. In this study, the in vitro effects of DZO 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 DZO leads to a decrease in cAMP concentration and an increase in basal IP3 levels. However, DZO does not affect basal levels of JAK1 and STAT3 phosphorylation. Instead, DZO inhibits leukocyte responsiveness to PMA and ionomycin, substances that, under normal conditions, enhance JAK/STAT signaling. These findings demonstrate that DZO significantly affects key molecular parameters related to cell signaling.

Organophosphorus pesticide exposure from house dust and parent-reported child behavior in Latino children from an orchard community.

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 (ß=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.

Acetylcholine triggered enzymatic cascade reaction based on Fe7S8 nanoflakes catalysis for organophosphorus pesticides visual detection.

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 Fe7S8 nanoflakes (Fe7S8 NFs), we propose an OPs detection method that rationally integrated Fe7S8 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 H2O2 to suppress the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) that catalyzed by Fe7S8 NFs. Benefiting from the integration of Fe7S8 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.

Unlocking the interaction of organophosphorus pesticide residues with ecosystem: Toxicity and bioremediation.

Organophosphorus adulteration in the environment creates terrestrial and aquatic pollution. It causes acute and subacute toxicity in plants, humans, insects, and animals. Due to the excessive use of organophosphorus pesticides, there is a need to develop environmentally friendly, economical, and bio-based strategies. The microbiomes, that exist in the soil, can reduce the devastating effects of organophosphates. The use of cell-free enzymes and yeast is also an advanced method for the degradation of organophosphates. Plant-friendly bacterial strains, that exist in the soil, can help to degrade these contaminants by oxidation-reduction reactions, enzymatic breakdown, and adsorption. The bacterial strains mostly from the genus Bacillus, Pseudomonas, Acinetobacter, Agrobacterium, and Rhizobium have the ability to hydrolyze the bonds of organophosphate compounds like profenofos, quinalphos, malathion, methyl-parathion, and chlorpyrifos. The native bacterial strains also promote the growth abilities of plants and help in detoxification of organophosphate residues. This bioremediation technique is easy to use, relatively cost-effective, very efficient, and ensures the safety of the environment. This review covers the literature gap by describing the major effects of organophosphates on the ecosystem and their bioremediation by using native bacterial strains.

A Multienzyme Reaction-Mediated Electrochemical Biosensor for Sensitive Detection of Organophosphorus Pesticides.

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 Fe3O4@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 H2O2 in an electrolytic cell. Fe3O4@Au-Pt has excellent peroxidase-like activity and can catalyze the oxidation of 3,3',5,5'-tetramethvlbenzidine (TMB) in the presence of H2O2, 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.

Distribution of organophosphorus pesticides and its potential connection with probiotics in sediments of a shallow freshwater lake.

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.

Ecological risk assessment for typical organophosphorus pesticides in surface water of China based on a species sensitivity distribution model.

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 (HC5) 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 HC5 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.

Compatibility of cloud point extraction with gas chromatography: Matrix effects of Triton X-100 on GC-MS and GC-MS/MS analysis of organochlorine and organophosphorus pesticides.

Cloud point extraction is an environmentally benign and simple separation/concentration procedure that can be regarded as an alternative to classical liquid-liquid extraction. In the current work, it was studied the compatibility of cloud point extraction followed by back-extraction in low volume of organic solvent with gas chromatography-mass spectrometry (GC-MS and GC-MS/MS). Triton X-100 was preferred than Triton X-114 as a surfactant to produce the clouding phenomenon and hexane or isooctane was found to be appropriate organic solvents which can be used at the back-extraction step. It was observed that ca. 0.09 % w/w Triton X-100 was co-extracted in the organic phase (hexane or isooctane) so further study was carried out to find out its effect on the GC-MS (GC-MS/MS) measurement when liquid samples are injected without any pre-cleaning to remove the surfactant. The chromatographic separation and the mass detection were not deteriorated by the concomitant Triton X-100 for analysis of several Organochlorine and Organophosphorus pesticides (alpha-HCH, beta-HCH, gamma-HCH, Pentachlorobenzene, Hexachlorobenzene, Chlorpyrifos, Chlorpyrifos-methyl, Aldrin, Endrin, Dieldrin, alpha-Endosulfan, Heptachlor, Heptachlor-endo-epoxide-A, o,p-DDD, p,p-DDD, o,p-DDE, p,p-DDE, o,p-DDT and p,p-DDT). The stability of the GC system when introducing surfactant was assessed as acceptable (typically the peak area RSD% for 20 consecutive injections were below 5 %). Under the developed vaporization conditions using PTV or PSS injectors it can be deduced that Triton X-100 is deposited on the inner surface of the liner. This effect is beneficial since the resulting surfactant layer makes a surface which facilitates the pesticides transfer to the GC column. As a consequence, for some analytes, a substantial enhancement (up to 2.3 times) in the sensitivity was observed when the matrix-matched medium (0.09 % w/w Triton X-100 in organic solvent) is used compared to calibration in solely hexane or isooctane. Meanwhile, the measurement precision in the presence of Triton X-100 remains unchanged. The GC-MS/MS analysis was alternatively accomplished by the use of glass or metal liner and it was found that the glass one should be preferable. Finally, it can be concluded that cloud point extraction with Triton X-100 can be combined with GC-MS or GC-MS/MS analysis by applying liquid injection of the target analytes transferred in organic solvents such as hexane or isooctane. We have established a positive effect of Triton X-100 on the instrumental performance which is on opposite to the generally accepted concern of the negative influence of the surfactants on the gas chromatographic analysis.

Metal-pyrimidine nanocubes immobilized enzymes with pH-switchable multienzyme-like activity for broad-pH-responsive sensing assay for organophosphorus pesticides.

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 Cu2+. 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 H2O2. 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 H2O2 to •OH and O2, 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.

Organophosphorus pesticide contaminants in fruits and vegetables: A meta-analysis.

The worldwide demand for organophosphorus pesticides (OPs) in food production has raised concerns about pesticide residues. Meta-analysis, proven effective in assessing contaminants like aflatoxins and organotin compounds, is applied here to comprehensively study OP contamination in fresh fruits and vegetables. Employing Comprehensive Meta-Analysis V3.0 software, we meticulously examined 24 relevant articles encompassing 69,467 data points. Our findings revealed that while the residual concentrations of OPs (such as chlorpyrifos and profenofos) in most fruits and vegetables have typically met international or national safety standards, including Codex Alimentarius Commission, European Union, British, and Chinese standards, there are some instances in which the maximum residue limits have been exceeded, posing safety risks. Therefore, significant efforts are required to maintain residual OP contamination at safe concentrations.

Sensitive fluorescent detection of phosmet and chlortetracycline in animal-derived food samples based on a water-stable Cd(II) chain-based zwitterionic metal-organic framework.

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.

Accumulation of organophosphorus pollutants in adipose tissue of obese women - metabolic alterations.

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.

Introducing Mn into ZIF-8 nanozyme for enhancing its catalytic activities and adding specific recognizer for detection of organophosphorus pesticides.

In order to design and establish a highly efficient and selective nanozyme-based sensing platform for the UV-vis detection of organophosphorus pesticides (OPs), Mn was introduced into ZIF-8 nanozyme for enhancing its catalytic activities and adding specific recognizer. The Mn-doped ZIF-8 (Mn-ZIF-8) nanocomposites were synthesized with a very facile one-pot method by heating the mixture of ZnO, 2-methylimidazole (Hmin) and Mn(CH3COO)2·4H2O in a solvent-free system at 180 °C for 8 h. The Mn-ZIF-8 nanocomposite showed a higher peroxidase activity and an additional thiocholine (TCh)-degradable property compared to the pristine ZIF-8. OPs could inhibit acetylcholinesterase (AChE) to catalyze the hydrolysis of acetylthiocholine (ATCh) to produce TCh, thus blocking the degradation of Mn-ZIF-8 and protecting the catalysis of the oxidation of colorless 3,3',5,5'-tetramethylbenzydine (TMB) to blue oxidized TMB (ox-TMB). Accordingly, a detection method for OPs with high sensitivity and selectivity was designed and established on the basis of the Mn-ZIF-8 nanozyme with a linear range of 0.1-20 nM and a limit of detection (LOD) as low as 54 pM.

Development of a carbon quantum dot-based sensor for the detection of acetylcholinesterase and the organophosphate pesticide.

In this study, a proper and reliable fluorometric method is introduced for screening acetylcholinesterase (AChE) and its inhibitors, using carbon quantum dots (CQDs) as the signal reporter. Pure, S-doped, and P-doped CQDs, were synthesized and their recoverable fluorescence quenching properties were observed, when exposed to Hg2+, Cu2+, and Fe3+ quenching ions, respectively. The study on the recovery of their emission showed that after the introduction of another guest substance with a stronger affinity to the quenching ions, their fluorescence is restored. The Design Expert software was employed to compare the performance of the three CQDs, as fluorescent probes, based on their quenching efficiency and the percentage of their emission recovery in the presence of AChE and acetylthiocholine (ATCh). Based on the statistical analysis, among the studied CQDs, S-doped CQD was the most suitable candidate for sensor designing. The detection mechanism for the proposed S-doped CQD-based sensor is as follows: The strong binding of Cu2+ ions to carboxyl groups of S-doped CQD quenches the fluorescence signal. Then, hydrolysis of ATCh into thiocholine (TCh) in the presence of AChE causes fluorescence recovery, due to the stronger affinity of Cu2+ to the TCh, rather than the CQD. Finally, in the presence of malathion and chlorpyrifos inhibitors, AChE loses its ability to hydrolyze ATCh to TCh, so the fluorescence emission remains quenched. Based on the proposed detection technique, the designed sensor showed detection limits of 1.70 ppb and 1.50 ppb for malathion and chlorpyrifos, respectively.

Preparation of black phosphorus nanosheets/ zeolitic imidazolate framework nanocomposite for high-performance solid-phase microextraction of organophosphorus pesticides.

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.

A Multi-Enzyme Cascade Response for the Colorimetric Recognition of Organophosphorus Pesticides Utilizing Core-Shell Pd@Pt Nanoparticles with High Peroxidase-like Activity.

In modern agricultural practices, organophosphorus pesticides or insecticides (OPs) are regularly used to restrain pests. Their limits are closely monitored since their residual hinders the capability of acetylcholinesterase (AChE) and brings out a threatening accumulation of the neurotransmitter acetylcholine (ACh), which affects human well-being. Therefore, spotting OPs in food and the environment is compulsory to prevent human health. Several techniques are available to identify OPs but encounter shortcomings like time-consuming, operating costs, and slow results achievement, which calls for further solutions. Herein, we present a rapid colorimetric sensor for quantifying OPs in foods using TMB as a substrate, a multi-enzyme cascade system, and the synergistic property of core-shell Palladinum@Platinum (Pd@Pt) nanoparticles. The multi-enzyme cascade response framework is a straightforward and effective strategy for OPs recognition and can resolve the previously mentioned concerns. Numerous OPs, including Carbofuran, Malathion, Parathion, Phoxim, Rojor, and Phosmet, were successfully quantified at different concentrations. The cascade method established using Pd@Pt had a simple and easy operation, a lower detection limit range of (1-2.5 ng/mL), and a short detection time of about 50 min. With an R2 value of over 0.93, OPs showed a linear range of 10-200 ng/mL, portraying its achievement in quantifying pesticide residue. Lastly, the approach was utilized in food samples and recovered more than 80% of the residual OPs.