Novel electrochemiluminescence sensing platform for ultrasensitive detection of malathion residue in tea based on SiO2NSs doped Luminol/AgNPs as a signal amplification strategy.

To address the potential hazards of organophosphorus pesticides (OPs) residues in tea, an electrochemiluminescence (ECL) aptasensor based on functionalized nanomaterials was constructed in this work. Firstly, gold nanoparticles (AuNPs) were attached on the surface of multi-walled carbon nanotubes (MWCNTs) by the constant potential electrodeposition to form a compound, and it was utilized to provide excellent immobilization sites for complementary DNA (cDNA). Subsequently, composite nanomaterials were synthesized by a one-pot method with aminated Luminol/silver nanoparticles@silica nanospheres (NH2-Luminol/Ag@SiO2NSs). Finally, NH2-Luminol/Ag@SiO2NSs was combined with a malathion aptamer (Apt) to obtain signal probes (SPs) for the construction of an aptasensor. The aptasensor had a wide linear range (1×10-3-1×103 ng/mL) and a low limit of detection (LOD) (0.3×10-3 ng/mL). It had the virtues of high sensitivity, wonderful stability and excellent specificity, which could be used for the detection of malathion residue in tea. The work provides a proven way for the construction of a rapid and ultrasensitive aptasensor with low-cost.

Single-atom Zr-doped CoOOH with enhanced electrical conductivity as a signal amplifier and detection probe for the indirect non-enzymatic electrochemical determination of malathion in foods.

Herein, a novel electrochemical sensor based on zirconium-doped cobalt oxyhydroxide (ZrCoOOH) was proposed for highly sensitive non-enzymatic determination of malathion (MAL). The doping of Zr can improve the electrical conductivity of CoOOH, of which the transfer resistance was reduced from 241.1 Ω to 140.2 Ω. Furthermore, the X-ray photoelectron spectroscopy confirmed that part of Co2+ was converted to Co3+ due to the introduction of Zr. The Co3+ in ZrCoOOH could react with MAL to form Co2+, which enhanced the electrooxidation current of Co2+. Therefore, the peak current of Co2+ was served as detection probe for MAL. Under optimal conditions, the developed sensor established the linear relationship for MAL in the concentration range of 0.001-10.0 µM with a low limit of detection (0.64 nM). The constructed sensor was employed to detect MAL in food samples (peach, kiwi fruit, spinach and tomato), verifying the accuracy and practicability of the sensor.

Covalent adduct formation of histone with organophosphorus pesticides in vitro.

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.

Superior oxidase-mimetic activity of FeCo-NC dual-atom nanozyme for smartphone-based visually colorimetric assay of organophosphorus pesticides.

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

Overexpression of an Integument Esterase Gene LbEST-inte4 Infers the Malathion Detoxification in Liposcelis bostrychophila (Psocoptera: Liposcelididae).

Liposcelis bostrychophila, commonly known as booklouse, is an important stored-product pest worldwide. Studies have demonstrated that booklices have developed resistance to several insecticides. In this study, an integument esterase gene, LbEST-inte4, with upregulated expression, was characterized in L. bostrychophila. Knockdown of LbEST-inte4 resulted in a substantial increase in the booklice susceptibility to malathion. Overexpression of LbEST-inte4 in Drosophila melanogaster significantly enhanced its malathion tolerance. Molecular modeling and docking analysis suggested potential interactions between LbEST-inte4 and malathion. When overexpressed LbEST-inte4 in Sf9 cells, a notable elevation in esterase activity and malathion tolerance was observed. HPLC analysis indicated that the LbEST-inte4 enzyme could effectively degrade malathion. Taken together, the upregulated LbEST-inte4 appears to contribute to malathion tolerance in L. bostrychophila by facilitating the depletion of malathion. This study elucidates the molecular mechanism underlying malathion detoxification and provides the foundations for the development of effective prevention and control measures against psocids.

Ecotoxicological strategies employing biochemical markers and organisms to monitor the efficacy of malathion photolysis treatment.

The objective of this study was to assess the photolysis-mediated degradation of malathion in standard and commercial formulations, and to determine the toxicity of these degraded formulations. Degradation tests were carried out with 500 µg L-1 of malathion and repeated three times. The initial and residual toxicity was assessed by using Lactuca sativa seeds for phytotoxicity, Stegomyia aegypti larvae for acute toxicity, and Stegomyia aegypti mosquitoes (cultivated from the larval stage until emergence as mosquitoes) to evaluate the biochemical markers of sublethal concentrations. For the standard formulations the photolytic process efficiently reduced the initial concentration of malathion to levels below the regulatory limits however, the formation of byproducts was revealed by chromatography, which allowed for a more complete proposal of photolytic-mediated malathion degradation route. The degraded formulations inhibited the growth of L. sativa seeds, while only the untreated formulations showed larvicidal activity and mortality. Both formulations slightly inhibited acetylcholinesterase activity in S. aegypti mosquitoes, while the standard formulation decreased and the commercial formulation increased glutathione S-transferase activity. However, there were no significant differences for superoxide dismutase, esterase-α, esterase-ß and lipid peroxidation. These findings indicate that in the absence of the target compound, the presence of byproducts can alter the enzymatic activity. In general, photolysis effectively degrade malathion lower than the legislation values; however, longer treatment times must be evaluated for the commercial formulation.

Ecological threat caused by malathion and its chiral metabolite in a honey bee-rape system: Stereoselective exposure risk and the mechanism revealed by proteome.

Honey bees play an important role in the ecological environment. Regrettably, a decline in honey bee colonies caused by chemical insecticides has occurred throughout the world. Potential stereoselective toxicity of chiral insecticides may be a hidden source of danger to bee colonies. In this study, the stereoselective exposure risk and mechanism of malathion and its chiral metabolite malaoxon were investigated. The absolute configurations were identified using an electron circular dichroism (ECD) model. Ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was used for chiral separation. In pollen, the initial residues of malathion and malaoxon enantiomers were 3571-3619 and 397-402 µg/kg, respectively, and R-malathion degraded relatively slowly. The oral LD50 values of R-malathion and S-malathion were 0.187 and 0.912 µg/bee with 5 times difference, respectively, and the malaoxon values were 0.633 and 0.766 µg/bee. The Pollen Hazard Quotient (PHQ) was used to evaluate exposure risk. R-malathion showed a higher risk. An analysis of the proteome, including Gene Ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG), and subcellular localization, indicated that energy metabolism and neurotransmitter transport were the main affected pathways. Our results provide a new scheme for the evaluation of the stereoselective exposure risk of chiral pesticides to honey bees.

Dissecting the Enantioselective Neurotoxicity of Isocarbophos: Chiral Insight from Cellular, Molecular, and Computational Investigations.

Chiral organophosphorus pollutants are found abundantly in the environment, but the neurotoxicity risks of these asymmetric chemicals to human health have not been fully assessed. Using cellular, molecular, and computational toxicology methods, this story is to explore the static and dynamic toxic actions and its stereoselective differences of chiral isocarbophos toward SH-SY5Y nerve cells mediated by acetylcholinesterase (AChE) and further dissect the microscopic basis of enantioselective neurotoxicity. Cell-based assays indicate that chiral isocarbophos exhibits strong enantioselectivity in the inhibition of the survival rates of SH-SY5Y cells and the intracellular AChE activity, and the cytotoxicity of (S)-isocarbophos is significantly greater than that of (R)-isocarbophos. The inhibitory effects of isocarbophos enantiomers on the intracellular AChE activity are dose-dependent, and the half-maximal inhibitory concentrations (IC50) of (R)-/(S)-isocarbophos are 6.179/1.753 µM, respectively. Molecular experiments explain the results of cellular assays, namely, the stereoselective toxic actions of isocarbophos enantiomers on SH-SY5Y cells are stemmed from the differences in bioaffinities between isocarbophos enantiomers and neuronal AChE. In the meantime, the modes of neurotoxic actions display that the key amino acid residues formed strong noncovalent interactions are obviously different, which are related closely to the molecular structural rigidity of chiral isocarbophos and the conformational dynamics and flexibility of the substrate binding domain in neuronal AChE. Still, we observed that the stable "sandwich-type π-π stacking" fashioned between isocarbophos enantiomers and aromatic Trp-86 and Tyr-337 residues is crucial, which notably reduces the van der Waals' contribution (ΔGvdW) in the AChE-(S)-isocarbophos complexes and induces the disparities in free energies during the enantioselective neurotoxic conjugations and thus elucidating that (S)-isocarbophos mediated by synaptic AChE has a strong toxic effect on SH-SY5Y neuronal cells. Clearly, this effort can provide experimental insights for evaluating the neurotoxicity risks of human exposure to chiral organophosphates from macroscopic to microscopic levels.

Biodegradation of malathion by Micrococcus sp. strain MAGK3: kinetics and degradation fragments.

Malathion is widely used as an agricultural insecticide, but its toxic nature makes it a serious environmental contaminant. To screen indigenous bacteria for malathion degradation, a strain MAGK3 capable of utilizing malathion as its sole carbon and energy source was isolated from Pennisetum glaucum agricultural soil. Based on morphological and biochemical characteristics and 16S rDNA sequence analysis, strain MAGK3 was identified as Micrococcus aloeverae. The strain was cultured in the presence of malathion under aerobic and energy-restricting conditions, and it grew well in MSM containing malathion (1000 µl/L), showing the highest specific growth rate at 500 µl/L. Reverse-phase UHPLC-DAD analysis indicated that 100%, 90.48%, 84.27%, 75.46%, 66.65%, and 31.96% of malathion were degraded within 15 days in liquid culture augmented with 50, 100, 200, 300, 500, and 1000 µl/L concentrations of commercial malathion, respectively. Confirmation of malathion degradation to malathion mono, diacids, and phosphorus moiety was performed by Q-TOF-MS analysis, and a pathway of biodegradation was proposed. The influence of co-substrates was also examined to optimize biodegradation further. Kinetic studies based on different models were conducted, and the results demonstrated good conformity with the first-order model. Malathion degradation process by Micrococcus aloeverae was characterized by R2 of 0.95, and the initial concentration was reduced by 50% i.e. (DT50) in 8.11 d at an initial concentration of 500 µl/L. This establishes the Micrococcus sp. as a potent candidate for active bioremediation of malathion in liquid cultures as it can withstand high malathion load and can possibly impact the development strategies of bioremediation for its elimination.

Ultrasensitive zero-background photoelectrochemical biosensor for analysis of organophosphorus pesticide based on in situ formation of DNA-templated Ag2S photoactive materials.

Herein, a novel signal-on photoelectrochemical (PEC) biosensor with nearly zero background noise (ZBN) was first fabricated to determine the presence of organophosphorus pesticide based on in situ formation of DNA-templated Ag2S photoactive materials, accompanied by hybridization chain reaction (HCR) signal amplification. The capture probe (S1) on the gold nanoparticle-modified electrode can hybridize with the aptamer molecule to generate a simple PEC biosensor. In the presence of a target molecule, the aptamer molecule is released on the double-stranded DNA (dsDNA)-modified PEC biosensor. Meanwhile, the capture probe remains on the electrode and can open the DNA hairpins (H1, H2) which are rich in cytosine, to trigger the HCR reaction. The rich "C" strands are uncovered after formation of a long dsDNA polymer strand, which can assemble multiple silver ions (Ag+) by means of by C-Ag+-C chelation. Then, a large number of Ag2S can be generated by challenging with S2- solution, producing a satisfactory photocurrent signal. The photoactive material is formed in situ, which eliminates the laborious operation. Moreover, the signal can be highly amplified with nearly zero background noise and HCR signal amplification. Under optimal conditions, the ZBN aptasensor exhibited high sensitivity and selectivity, with a low detection limit of 2 pg mL-1 for malathion. Importantly, the sensing platform can also be applied to determine the presence of malathion in real samples. In this assay, a novel signal-on photoelectrochemical biosensor with nearly zero background noise was first fabricated to determine the presence of organophosphorus pesticide based on in situ formation of DNA-templated Ag2S photoactive materials, accompanied by hybridization chain reaction signal amplification.

Nuclear magnetic resonance chiral discrimination of fipronil and malathion agrochemicals: A case study.

The aim of the present study was to optimize a protocol for nuclear magnetic resonance (NMR) chiral discrimination to be used to determine the enantiomers ratio of agrochemicals. For this goal, the commercial agrochemicals fipronil and malathion were employed as active targets due the distinct physicochemical properties. We used the cyclodextrins to evaluate the chiral discrimination in aqueous media and chiral solvent agents to check in organic media. The fipronil chiral discrimination was accessed by ß-CD in aqueous solution, although this procedure was ineffective for malathion due the low solubility. In organic media, the NMR chiral discrimination was successful for both agrochemicals and sensitive to dilution process. The NMR experiments explore very sensitive nuclei, for instance 1 H, 19 F, and 31 P, in a simple, practical and low residue experimental protocol.

Effect of storage states on stability of three organophosphorus insecticide residues on cowpea samples.

BACKGROUND: The stability of pesticide residues in stored samples is very important to ensure the quality of data about the residues. The evaluation of pesticide residues in food and environment samples is an important means to ensure food quality and protect consumers against potential dietary risks. Improper storage of pesticide residue samples may result in loss of pesticide and unreliable data, which could affect safety assessments. RESULTS: The influences of storage conditions, including temperature (-20 °C, 4 °C, and ambient temperature) and sample state (homogenized state and coarsely chopped state) on the storage stability of dichlorvos, malathion, and diazinon on cowpea were studied. Dichlorvos and malathion were more stable in an homogenized state than in a coarsely chopped state. At 4 °C, the residual dichlorvos in the coarsely chopped state and the homogenized state, respectively, was 12% and 69%; the residual malathion was 26% and 92%, respectively. Dichlorvos suffered a large loss of 89% and 59% for coarsely chopped and homogenized cowpea, even at -20 °C. It was obvious that the stability of dichlorvos and malathion were more affected by storage state than diazinon. The stability of diazinon was significantly affected by temperature. The effect of storage state and temperature on stability is likely to be correlated with enzymes in the matrix, such as superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD). CONCLUSION: The optimal stable storage conditions for three organophosphorus insecticides residues on cowpea were in the homogenized state and under a lower temperature. © 2021 Society of Chemical Industry.

Effect of dielectric barrier discharge plasma on the degradation of malathion and chlorpyrifos on lettuce.

BACKGROUND: Pesticides have been widely used to control pests on agricultural products in China, and large amounts of pesticide residues have caused a serious threat to human health. Thus, developing a high-efficiency pesticide degradation method for fresh vegetables represents a great challenge. The present study investigated the effects of dielectric barrier discharge (DBD) plasma on the degradation of malathion and chlorpyrifos in aqueous solutions and on lettuces. RESULTS: DBD treatment significantly degraded malathion and chlorpyrifos in water and on lettuce. After cold plasma treatment at 80 kV for 180 s, the degradation efficiency of malathion (0.5 µg mL-1 ) and chlorpyrifos (1.0 µg mL-1 ) in aqueous solutions reached 64.6% and 62.7%, respectively. The degradation intermediates were explored by HPLC-mass spectrometry and the DBD plasma degradation pathways of malathion and chlorpyrifos were proposed. There was no significant damage to the quality of lettuces, including color and chlorophyll content, after plasma treatment. Ascorbic acid decreased significantly during long-term treatment with DBD plasma. To ensure the quality of lettuces during processing, the treatment time was shortened to 120 s. Under this condition, the degradation efficiency of malathion (0.5 mg kg-1 ) and chlorpyrifos (1.0 mg kg-1 ) on lettuces was found to be 53.1% and 51.4%. More importantly, we noted that cold plasma treatment significantly inactivated the microorganisms on lettuces. CONCLUSION: The results of the present study show that cold plasma is an effective and safe method for the degradation of organic pesticide residues on fresh vegetables at the same time as retaining the original quality. © 2020 Society of Chemical Industry.

Glove performance in a warming climate: The role of glove material and climate on permeation resistance to organophosphate insecticides.

Hands and forearms are the principal sites of dermal exposure to organophosphate insecticides, which makes glove use one of the most important components of an exposure control strategy. However, the selection of suitable gloves depends on issues such as task, type, and concentration of organophosphate as well as cost. In addition, chemical protection performance of gloves may be temperature dependent, which is of increasing concern in a warming climate. Two recommended reusable glove materials (polyvinylchloride and nitrile butadiene rubber) and one single-use glove (nitrile/neoprene) were tested for permeation resistance to actual formulations of organophosphate insecticides with active ingredients dimethoate and malathion. Chemical resistance parameters were measured using American society for testing and materials permeation test cells and compared across glove, organophosphate type, and temperature. The three gloves demonstrated comparable and adequate chemical resistance (less than one µg cm-2 min-1 for up to 8 hr exposure; 25-60 °C) for dilute forms of dimethoate and malathion, used during spraying activities. However, the single-use nitrile/neoprene glove is not designed to fully cover the elbow which limits its suitability. In permeation tests that reflect "worst case" exposure scenario to concentrated (neat) organophosphate formulations, as in mixing/loading tasks, a significant variation in chemical resistance between gloves was observed. While polyvinylchloride offered the maximum resistance, physical degradation of nitrile butadiene rubber after 3 hr of continuous exposure makes it unsuitable for handling neat dimethoate. The single-use nitrile/neoprene glove material had considerably poorer permeation resistance (up to 155-fold greater permeation and 6-fold shorter breakthrough) against neat formulations. Overall, elevated temperature (>40 °C) was shown to result in significantly greater (P < 0.05) cumulative permeation of neat formulation insecticides. This work demonstrates the variation in glove performance and potential for greater exposure risk particularly when mixing concentrated pesticides at elevated temperature conditions such as an occluded human skin or hot greenhouses. Training and guidance on testing, selection, use, and storage of gloves should consider in-use exposure scenarios and temperature-induced reduction in chemical protective performance.

Ozone treatment pak choi for the removal of malathion and carbosulfan pesticide residues.

Since the beginning of the widespread use of pesticides, their removal from food has become a serious concern. In this study, the removal of residual pesticides (malathion and carbosulfan) from pak choi via treatment with ozonated water was investigated. Under the optimal treatment conditions, i.e., 2.0 mg/L ozonated water and a treatment duration of 15 min, malathion and carbosulfan were degraded by 53.0 and 33.0%, respectively, without any significant changes in color. Even though there was a slight decrease in vitamin C content (~7.9 mg/100 g) following the treatments, a significant decrease in the microbial colonies on the vegetables was observed. Additionally, the pesticide degradation mechanism showed good fitting with a "first + first"-order kinetic model (R2 > 0.9), and the slope (k) indicated that ozone had a more prominent degradation effect on malathion than on carbosulfan. Therefore, this study provides a theoretical basis for controlling agricultural pesticide residues in household applications.

Degradation Trends of Some Insecticides and Microbial Changes during Sauerkraut Fermentation under Laboratory Conditions.

The aim of this study was to monitor the degradation of three insecticides licensed for the control of cabbage moths during the 14-day fermentation period of sauerkraut samples. The hypothesis of this study is that the different sauerkraut fermentation processes could affect the degradation of applied insecticides. For this purpose, the fresh cabbage leaves contaminated with (λ-cyhalothrin, malathion, and chlorpyrifos-methyl) were left for fermentation with and without (natural) starter addition (Lactobacillus plantarum 112), and vacuum-packed as a control under laboratory conditions. The pH values and microbial growth were periodically monitored in sauerkraut samples during the fermentation period. During this time, the insecticide residues were determined in control and treatment samples using LC-MS-MS. In control samples, the degradation of chlorpyrifos-methyl and malathion was higher with rates of 69 and 98%, respectively, compared with the sauerkraut samples (12 and 59%; 31 and 34%, respectively) 14 days after the insecticide application. At the end of fermentation (14 d), no significant reduction in λ-cyhalothrin was detected in both treatments and control (13-19% reduction). The current study demonstrated that the presence of the lactic acid bacteria in the sauerkraut fermentation accelerated pH decline (below 4.0), and these fermentation conditions probably decelerated the degradation of malathion and chlorpyrifos-methyl. The results showed that the stability of different insecticides varied during the same fermentation process.

The stability of four organophosphorus insecticides in stored cucumber samples is affected by additives.

The influence of some additives, including metal ions, antioxidants, enzyme inhibitors and organic solvents, on the storage stability of four organophosphorus pesticides in cucumber samples were investigated. It was found that metal ions, including Al3+, Fe3+, and Co2+, increased the stability of dichlorvos, malathion, and chlorpyrifos. Conversely, Al3+, Fe3+, Fe2+, and Co2+ caused catalytic degradation of diazinon. With the addition of organic solvents (CH2Cl2, CHCl3, CCl4, CH3OH and CH3COCH3), remaining of diazinon residues was higher (16-54%) after storage for seven days. CCl4 was associated with the highest retention of malathion, diazinon, and chlorpyrifos (33%, 48% and 44%, respectively) in samples. SDS also stabilized the pesticides since residues were, again, higher (13-38%) after seven days storage. Furthermore, addition of Al3+ and Fe3+ decreased peroxidase (POD) activity and inhibited degradation of dichlorvos and malathion. After 14 days, lyophilization increased the pesticide residues remaining by 36%, 29%, and 58% for diazinon, malathion and chlorpyrifos, respectively. Overall, the stability of these pesticides during storage is impacted by water content and addition of exogenous substances. This could ensure higher quality of pesticide residue data in samples.

Rolling circle amplification promoted magneto-controlled photoelectrochemical biosensor for organophosphorus pesticides based on dissolution of core-shell MnO2 nanoflower@CdS mediated by butyrylcholinesterase.

A photoelectrochemical (PEC) aptasensing platform is devised for sensitive detection of an organophosphorus pesticide based on dissolution of core-shell MnO2 nanoflower@CdS (MnO2 NF@CdS) by thiocholine (TCh). TCH is produced from the butyrylcholinesterase-acetylthiocholine system, accompanied by target-triggered rolling circle amplification (RCA). The core-shell MnO2 NF@CdS with excellent PEC performance was synthesized and employed as a photo-sensing platform. The target was detected on a functionalized magnetic probe with the corresponding aptamer. Upon malathion introduction, the aptamer was detached from the magnetic beads, while capture DNA (cDNA, with primer fragment) remained on the beads. The primer fragment in cDNA can trigger the RCA reaction to form a long single-stranded DNA (ssDNA). Furthermore, a large number of butyrylcholinesterase (BChE) were assembled on the long ssDNA strands through the hybridization with the S2-Au-BChE probe. Thereafter, TCh generated from hydrolysis of ATCh by BChE can reduce MnO2 NF (core) to Mn2+ and release the CdS nanoparticles (shell) from the platform electrode, significantly enhancing the PEC signal. Under optimal conditions, the proposed aptasensor exhibited high sensitivity for malathion with a low detection limit of 0.68 pg mL-1. Meanwhile, it also presents outstanding specificity, reproducibility, and stability. Importantly, the sensing platform provides a new concept for detection of pesticide. Graphical abstract Herein, this work devised a photoelectrochemical (PEC) aptasensing platform for sensitive detection of organophosphorus pesticide based on dissolution of core-shell MnO2 nanoflower@CdS (MnO2 NF@CdS) by the as-produced thiocholine (TCh) from the butyrylcholinesterase-acetylthiocholine system, accompanying with the target-triggered rolling circle amplification (RCA).

Effect of chlorination on anti-acetylcholinesterase activity of organophosphorus insecticide solutions and contributions of the parent insecticides and their oxons to the activity.

Organophosphorus insecticides are known to be partly transformed to their respective oxons during the chlorination step of drinking water treatment. For most organophosphorus insecticides, the toxicological endpoint for determining acceptable daily intake levels is inhibition of acetylcholinesterase (AChE). Like the parent insecticides, oxons also inhibit AChE, so the presence of oxons in drinking water is also evaluated. However, no attention is paid to the possible presence of transformation products (TPs) other than oxons. In the present study, we determined whether the anti-AChE activity observed for chlorinated solutions of the organophosphorus insecticides malathion and methidathion could be solely attributed to the parent compounds and their oxons. Upon chlorination, both malathion and methidathion were immediately transformed to their oxons; the maximum transformation ratios were 60% and 30%, respectively, indicating that at least 40% and 70% of these compounds were transformed into other TPs. Before chlorination, malathion- and methidathion-containing solutions exhibited little to no anti-AChE activity, but the solutions showed strong activity after chlorination. The contributions of the parent insecticides and their oxons to the activities of the chlorinated samples were calculated from the concentrations of the compounds in the samples and dose-response curves for chemical standards of the compounds. For both the malathion-containing solution and the methidathion-containing solution, the calculated anti-AChE activities were almost the same as the observed activities at every chlorination time. This suggests that the observed activities could be attributed solely to the parent insecticides and their oxons, indicating that other TPs need not be considered.

Enantiomeric separation of malathion and malaoxon and the chiral residue analysis in food and environmental matrix.

Malathion is a widely used chiral phosphorus insecticide, which has a more toxic chiral metabolite malaoxon. In this work, the enantiomers of malathion and malaoxon were separated by high-performance liquid chromatography-mass/mass (HPLC-MS/MS) with chiral columns using acetonitrile/water or methanol/water as mobile phase, and the chromatographic conditions were optimized. Based on the chiral separation, the chiral residue analysis methods for the enantiomers in soil, fruit, and vegetables were set up. Two pairs of the enantiomers were better separated on CHIRALPAK IC chiral column, and baseline simultaneous separations of malathion and malaoxon enantiomers were achieved with acetonitrile/water (40/60, v/v) as mobile phase at a flow rate of 0.5 mL/min. The elution orders were -/+ for both malathion and malaoxon measured by an optical rotation detector. The chiral residue analysis in soil, fruit, and vegetables was validated by linearity, recovery, precision, limit of detection (LOD), and limit of quantification (LOQ). The LODs and LOQs for the enantiomers of malathion were 1 µg/kg and 3-5 µg/kg and 0.08 µg/kg and 0.20-0.25 µg/kg for malaoxon enantiomers. Good linear calibration curves for each enantiomer in the matrices were obtained within the concentration range of 0.02-12 mg/L. The mean recoveries of the enantiomers of malathion and malaoxon ranged from 82.26% to 109.04%, with RSDs of 0.71-8.63%.The results confirmed that this method was capable of simultaneously determining the residue of malathion and malaoxon in food and environmental matrix on an enantiomeric level.