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.

Malathion detection based on polydopamine enhanced oxidase-mimetic activity of palladium nanocubes.

Nowadays, fabricating simple and efficient pesticide detection methods become a research focus due to the great threat pesticide residues posed to human health and environment. Herein, we constructed a high-efficiency and sensitive colorimetric detection platform for malathion detection based on polydopamine-dressed Pd nanocubes (PDA-Pd/NCs). The Pd/NCs coated with PDA exhibited excellent oxidase-like activity, which was attributed to the substrates accumulation and accelerated electron transfer induced by PDA. What's more, we successfully achieved sensitive detection of acid phosphatase (ACP) using 3,3',5,5'-tetramethylbenzidine (TMB) as the chromogenic substrate, relying on the satisfactory oxidase activity from PDA-Pd/NCs. However, the addition of malathion could inhibit the activity of ACP and limit the production of medium AA. Therefore, we constructed a colorimetric assay for malathion based on PDA-Pd/NCs + TMB + ACP system. The wide linear range (0-8 µM) and low detection limit (0.023 µM) indicate excellent analytical performance, which is superior to most malathion analysis methods previously reported. This work not only provides a new idea for dopamine coated nano-enzyme to improve its catalytic activity, but also creates a new tactics for the detection of pesticides such as malathion.

Nanozymes paper-based analytical device for the detection of organophosphate pesticides in fruits and vegetables.

In this work, copper oxide nanoparticles (CuONPs) nanozymes paper-based analytical device was designed for the rapid detection of organophosphate pesticides in fruits and vegetables. The paper-based analytical device was modified with silica oxide nanoparticles to enhance the assay sensitivity. CuO nanozymes displayed peroxidase-like activity and catalyzed the oxidation of o-dianisidine in the presence of H2O2 from the hydrolysis of acetylthiocholine. This results in the formation of a brown-colored product. In the presence of organophosphate pesticides such as malathion, acetylcholinesterase activity was inhibited, resulting in reduced color intensity production, and which was measured with a smartphone. The proposed nanozymes paper-based analytical device exhibited a good linear detection range (0.1-5 mg L-1), a low detection limit of 0.08 mg L-1, and the analysis time was only about 10 min for malathion detection under optimal conditions. Moreover, the CuONPs had excellent catalytic activity and higher stability than peroxidase. Finally, this device can be applied to detect organophosphate pesticides in fruits and vegetables with rapidity, accuracy, portability, and ease of handling in the field.

Bimetallic AuPt alloy/rod-like CeO2 nanojunctions with high peroxidase-like activity for colorimetric sensing of organophosphorus pesticides.

Organophosphorus pesticides (OP) have extensive applications in agriculture, while their overuse causes inevitable residues in food, soil, and water, ultimately being harmful to human health and even causing diverse dysfunctions. Herein, a novel colorimetric platform was established for quantitative determination of malathion based on peroxidase mimic AuPt alloy decorated on CeO2 nanorods (CeO2@AuPt NRs). The synthesized nanozyme oxidized colorless 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. Besides, the oxidized TMB was inversely reduced by ascorbic acid (AA), which were originated from hydrolysis of L-ascorbic acid-2-phosphate (AA2P) with the assistance of acid phosphatase (ACP). Based upon this observation ACP analysis was explored by colorimetry, showing a wid linear range of 0.2 ~ 3.5 U L-1 and a low limit of detection (LOD = 0.085 U L-1, S/N = 3). Furthermore, malathion present in the colorimetric system inhibited the activity of ACP and simultaneously affected the generation of AA, in turn promoting the recovery of the chromogenic reaction. Based on this, the LOD was decreased to 1.5 nM (S/N = 3) for the assay of malathion with a wide linear range of 6 ~ 100 nM. This simple colorimetric platform provides some informative guidelines for determination of other pesticides and disease markers.

Aptamer-based sensor for specific recognition of malathion in fruits and vegetables by surface-enhanced Raman spectroscopy and electrochemistry combination.

Aptamers are single-stranded DNA or RNA that can specifically bind to a target substance with high affinity. Pesticides have obvious biological effects and are very harmful to the human body and the environment. Surface-enhanced Raman spectroscopy (SERS) can be combined with aptamer for the rapid detection of pesticide residues because of its simple operation and high sensitivity. However, a single analysis method has certain limitations and can't satisfy the research of complex system. In this study, SERS and electrochemical were used to prove the specific recognition of malathion by aptamer. The biochemical sensor directly detected the SERS spectra of the aptamer, malathion, and aptamer-malathion through the SERS method. Malathion could also be verified the specific recognition of aptamer by differential pulse voltammetry (DPV) and cyclic voltammetry (CV). Based on the peak difference before and after the combination of malathion and aptamer, a detection method for the specific recognition of malathion in a complex system was established. The identification mechanism was discussed. Then, the practical detection of malathion demonstrated the practicability of the method. The method was applied for the detection of malathion in spiked apple and bell pepper samples. The recoveries were in the range of 89.80%-106.50%, and the relative standard deviations were from 2.51%-6.92%. The use of aptamers for the specific detection of pesticides will have the potential for broad applications in the future.

Risk assessment of organophosphorus pesticide residues in drinking water resources: Statistical and Monte-Carlo approach.

A large part of the world's agricultural production, despite its adverse effects on human health and water resources, depends on the use of pesticides. Despite strict regulations, the use of pesticides continues around the world. This study aimed to determine the residual concentrations of malathion and diazinon in samples of drinking water resources. To achieve this goal, 384 samples from 8 various sites from January to December 2020 were analyzed using gas chromatography (GC) with an electron capture detector (ECD) and liquid-liquid extraction technique. Besides, statistical analysis and a risk-modeling approach supported by an automatic Monte-Carlo procedure were applied. The results showed that there is a high carcinogenic risk regarding malathion and that the low age population is at the most non-carcinogenic risk regarding diazinon.

Degradation of malathion and carbosulfan by ozone water and analysis of their by-products.

BACKGROUND: Treatment by ozone water is an emerging technology for the degradation of pesticide residues in vegetables. The ozone dissolved in water generates hydroxyl radicals (· OH), which are highly effective in decomposing organic substances, such as malathion and carbosulfan. RESULTS: We found that washing pak choi with 2.0 mg L-1 ozone water for 30 min resulted in 58.3% and 38.2% degradation of the malathion and carbosulfan contents respectively, and the degradation rates of these pure pesticides were 83.0% and 66.3% respectively. In addition, the 'first + first'-order reaction kinetic model was found to predict the trend in the pesticide content during ozone water treatment. Based on investigations by gas chromatography-mass spectrometry combined with the structures of the pesticides, the by-products generated were identified. More specifically, the ozonation-based degradation of carbosulfan generated carbofuran and benzofuranol, whereas malathion produced succinic acid and phosphoric acid. Although some new harmful compounds were formed during degradation of the parent pesticides, these were only present in trace quantities and were transient intermediates that eventually disappeared during the reaction. CONCLUSION: Our results, therefore, indicate that ozone water treatment technology for pesticide residue degradation is worthy of popularization and application. © 2022 Society of Chemical Industry.

Viscose-derived activated carbons as adsorbents for malathion, dimethoate, and chlorpyrifos-screening, trends, and analysis.

The release and accumulation of pesticides in the environment require the development of novel sustainable technologies for their removal. While adsorption is a classical approach, the design of new materials with enhanced adsorption properties could rationalize the remediation routes and decrease potential risks for their non-target organisms, including humans. More importantly, the use of adsorbents and their synthesis should be implemented in a sustainable and environmentally friendly manner. In this contribution, we studied the adsorption of organophosphorus pesticides (OPs) dimethoate, malathion, and chlorpyrifos on viscose fiber-derived activated carbon fibers (ACFs). The most efficient adsorption was found for chlorpyrifos, followed by malathion and dimethoate, while material properties were correlated with OP uptake. These ACFs are extremely efficient for chlorpyrifos adsorption, with experimentally observed adsorption capacitances reaching 240 mg g-1. Detailed analysis suggests that chlorpyrifos is physisorbed on ACF surfaces and that increased surface hydrophilicity reduces the uptake. Studied ACFs have great potential for practical application. They can reduce OPs' concentrations to such levels that no acute neurotoxic effects of the studied OPs in spiked tap water samples are seen, even for starting concentrations up to 104 times higher than the allowed ones. Finally, this study presents possible guidance for developing even more efficient and environmentally friendly adsorbents for chlorpyrifos, the most toxic among studied OPs.

Peptide nanotube functionalized molecularly imprinted polydopamine based single-use sensor for impedimetric detection of malathion.

In the present study, a peptide nanotube functionalized polydopamine (p-Dop) based molecularly imprinted (MIP) sensor system was constructed, characterized, and studied for the impedimetric sensing of an organophosphorus pesticide, malathion (MLT). Electropolymerization in the presence of a template (MLT) was utilized as a convenient and effective strategy to generate imprinted p-Dop films on peptide nanotubes (PNTs) modified graphite electrodes (PGEs). Upon the removal of template, the adsorption of MLT on the specific cavities formed in the MIP film was tracked using electrochemical impedance spectroscopy (EIS). To attain optimal sensor response, experimental conditions, such as film thickness, analyte/functional monomer ratio, and desorption/adsorption time, were analyzed. The obtained MIP(p-Dop)-PNT-PGE sensor exhibited high sensitivity for electrochemical MLT analysis with a wide dynamic detection range of 13 pg mL-1 - 1.3 µg mL-1 and a LOD of 1.39 pg mL-1. The combination of a bio-inspired p-Dop-based MIP with the EIS technique allowed excellent sensitivity and selectivity toward MLT sensing which also yielded high recoveries in real samples. The success of this research strategy in real samples revealed its potential for various future environmental applications.

Porous polymers from octa(amino-phenyl)silsesquioxane and metalloporphyrin as peroxidase-mimicking enzyme for malathion colorimetric sensor.

Rapid and efficient pesticide detection methods are particularly important due to the growing problems of pesticide residues. Here, a new azo-based porous organic polymer, Azo(Fe)PPOP, was prepared from octa(amino-phenyl)silsesquioxane (OAPS) and iron(III) 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin (FeTPP(NO2)4) via a simple coupling reaction without the participation of metal catalysts. The inorganic cage units of OAPS endowed Azo(Fe)PPOP a porous framework, high surface area, favorably thermal and chemical stability. In Azo(Fe)PPOP, iron(III) porphyrin units were individually isolated in a fixed location, which could effectively avoid dimerization or self-oxidation as happens as in the case of porphyrin monomers. Such a unique structure made Azo(Fe)PPOP exhibit an excellent peroxidase-like catalytic performance in the presence of H2O2 and 3,3',5,5'-tetramethylbenzidine (TMB). Because of these advantages, we established a selective, facile, and sensitive colorimetric platform for direct detection of malathion within a very short time (3 min) with a low detection limit (8.5 nM). In addition, the recognition mechanism between Azo(Fe)PPOP and malathion was verified using X-ray photoelectron spectroscopy spectra. The practicality of the constructed platform was further executed by the detection of the pesticide in soil and food samples.

Assessing the atmospheric fate of pesticides used to control mosquito populations in Houston, TX.

During the summer months, urban areas are literal hot spots of mosquito-borne disease transmission and air pollution. Public health authorities release aerosolized pesticides directly into the atmosphere to help control adult mosquito populations and thereby reduce the threat of diseases, such as Zika Virus. The primary adulticides (i.e. pesticides used to control adult mosquito populations) in Houston, TX are permethrin and malathion. These adulticides are typically sprayed at night using ultra-low volume sprayers. Particulate matter (PM) samples including total suspended and fine PM (PM < 2.5 µm in aerodynamic diameter) were collected at four ground-based sites across Houston in 2013 and include daytime, nighttime, and 24 h samples. Malathion is initially sprayed as coarse aerosol (5-25 µm), but is measured in fine aerosol (<2.5 µm) and coarse aerosol in the urban atmosphere. Particle size is relevant both for deposition velocities and for human exposure. Atmospheric permethrin concentrations measured in nighttime samples peak at 60 ng m-3, while malathion nighttime concentrations peak near 40 ng m-3. Malaoxon, an oxidation product of malathion, was also frequently detected at concentrations >10 ng m-3, indicating significant nighttime oxidation. Based on the loss of malathion and the increase in malaoxon, the atmospheric half-life of malathion in Houston was estimated at <12 h, which was significantly shorter than previous half-life estimates (∼days). Importantly, malaoxon is estimated to be 22-33 times more toxic to humans than malathion. Both the aerosol size and the half-life are critical for mosquito control, human exposure, and risk assessment of these routine pesticides.

Paper-Based Enzymatic Colorimetric Assay for Rapid Malathion Detection.

Due to their unique properties, paper-based biosensors have attracted attention as inexpensive devices for on-site analysis. To achieve fast and sensitive detection of analytes, immobilization of enzymes with high apparent activities on paper is highly desirable; however, this is challenging. Herein, we report an improved approach to attach a malathion degrading enzyme, PoOPHM9, on paper via an interlocking network of Pluronic F127 (PF127)-poly(acrylic acid)-enzyme conjugates. The addition of PF127 improved retention of enzymatic activity as the apparent kinetic constant Vmax of the immobilized enzyme increased two-fold compared with the paper prepared without PF127. The PF127-poly(acrylic acid)-PoOPHM9 papers provided rapid colorimetric detection of malathion at 0.1-50 mM. The detection was completed within 5 min using a smartphone and image analysis software. As a proof-of-concept, malathion-contaminated water, plant, and apple samples were analyzed with the papers successfully. This material is promising for on-site rapid analysis of malathion-contaminated samples.

Determination of organophosphorus and synthetic pyrethroid pesticide residues and their variability in large size fruit crops.

BACKGROUND: Variability of pesticide residues in food item plays a key role for the evaluation of consumer food safety. However, variability factors (VFs) derived from the large size fruit crops are still scarce. Therefore, the present work was aimed to quantify pesticide residues and to estimate VFs in large size fruit crops of mango and guava. RESULTS: A total of 140 mango and 130 guava samples from different marketplaces in Bangladesh were collected to estimate the variability of pesticide residues (acephate, diazinon, malathion, fenitrothion, chlorpyrifos, quinalphos, dimethoate and cypermethrin) by in-house validated methods based on modified QuEChERS extraction and gas chromatography coupled with electron capture detector (ECD) and flame thermionic detector (FTD). The method was validated at three fortification levels (0.01, 0.10 and 0.30 mg kg-1 ) and satisfactory recoveries (80-111%) with relative standard deviation (RSDr ) ≤ 13% were achieved. A wide variation of residues was found in the analyzed samples. In the case of mango, the ranges of residues were 0.011-0.314, 0.015-0.04, and 0.05-0.291 mg kg-1 , respectively, for cypermethrin, chlorpyrifos, and dimethoate, while in the case of guava, the ranges were 0.04-0.113, and 0.03-0.290 mg kg-1 , respectively, for cypermethrin and acephate. The average VF for mango was 4.06 and it was 5.70 for guava. CONCLUSION: VFs originating from the marketed samples of mango and guava are reported in this study for the first time. The estimated VFs were higher than the default value of 3, therefore, the default VFs should be reconsidered when more data are obtained regarding large size crops. © 2021 Society of Chemical Industry.

Fluorescent and colorimetric dual-response sensor based on copper (II)-decorated graphitic carbon nitride nanosheets for detection of toxic organophosphorus.

An efficient and convenient detection method for organophosphorus pesticide (OP) residues is needed because of their high neurotoxicity and severe threat to food safety. OPs effectively reduce the production of thiocholine in the acetylcholinesterase/acetylthiocholine reaction by inhibiting the activity of acetylcholinesterase. Therefore, we developed a feasible and convenient fluorescent and colorimetric dual-response sensor based on the competitive complexation of Cu2+ between graphitic carbon nitride nanosheets and thiocholine for the rapid detection of OPs with high sensitivity. Malathion was used as a model OP, and a linear range of 70-800 nM with a detection limit of 6.798 nM for a fluorescent signaling platform and 2.5-25 nM with a detection limit of 1.204 nM for a colorimetric probe were attained. The constructed probe was successfully applied to determine OP in actual samples of cabbages leaves and tap water. The results indicated that the dual-response probe was reliable and sensitive to actual samples.

A fuzzy cognitive map approach to predict the hazardous effects of malathion to environment (air, water and soil).

Malathion is an organophosphorus insecticide and pesticide commonly used in crops and residential applications. The negative effects of Malathion on human health and ecosystems are of great concern. In this work, a mathematical model pivot on Fuzzy Cognitive Map (FCM) is used to analyse the causes and hazardous effects of Malathion to the environmental components (air, water and soil). Based on expert's opinion the possible factors that cause damage to health and ecosystems due to Malathion is identified, which serve as the input to the FCM. The FCM mathematically establishes the causal relation between these factors. The mathematical simulation is done by Python Programming. This approach can be used to study the interdependencies between the adverse effects of any pesticide in human health and environment due to prolonged exposure.

Fluorescence and colorimetric dual-mode sensor for visual detection of malathion in cabbage based on carbon quantum dots and gold nanoparticles.

A dual-mode fluorescence/colorimetric sensor based on carbon quantum dots (CQDs) and gold nanoparticles (GNPs) was developed for visual detection of malathion in cabbage. The CQDs-GNPs nanocomposite exhibited emission wavelength at 527 nm and absorption wavelength at 524 nm. The fluorescence intensity increased and absorption decreased with addition of malathion. Fluorescence and colorimetric calibration curves were established based on fluorescence intensity (R2 = 0.9914) and absorbance (R2 = 0.9608) in the range of 1 × 10-9-1 × 10-2 M, respectively. Furthermore, fluorescence and colorimetric standard arrays were prepared for visual detection of malathion according to the change of fluorescence brightness and color. Finally, the approximate concentrations of malathion in cabbage samples were estimated by the standard arrays and naked eyes. The calibration curves were used for accurate detection in cabbage samples with recoveries of 89.9%-103.4% (fluorescence) and 88.7%-107.6% (colorimetric). The established sensor for visual malathion detection in cabbage was accurate with strong application potential, especially for rapid screening.

Solvent-assisted dispersive liquid-solid phase extraction of organophosphorus pesticides using a polypyrrole thin film-coated porous composite magnetic sorbent prior to their determination with GC-MS/MS.

A porous composite magnetic sorbent was developed and used as a solid phase for the solvent-assisted preconcentration of organophosphorus pesticides. The hierarchical porous composite sorbent was composed of polypyrrole thin film coated on the surface of porous alginate beads with embedded magnetite nanoparticles. The pores in the alginate hydrogel beads were produced by carbon dioxide bubbles from the reaction of incorporated calcium carbonate with hydrochloric acid. The porous network was filled with dichloromethane to assist extraction. The fabricated porous composite sorbent was characterized and sorbent fabrication and extraction conditions were optimized to obtain the best extraction performance. The developed sorbent was coupled with GC-MS/MS to determine organophosphorus pesticides in fruit juices and vegetable. Under optimized condition, the developed method provided good linear range of 0.03-200 µg L-1 for dichlorvos, malathion, and fenthion, and 0.075-200 µg L-1 for mevinphos, dimethoate, and parathion methyl, respectively. Limits of detection were in the range 0.010 to 0.025 µg L-1. This method exhibited good relative recoveries in the range 84 to 99% and RSDs lower than 8%. The good stability of the sorbent enabled up to eight cycles of reuse.Graphical abstract.

Z-sep+ based QuEChERS technique for the pre-concentration of malathion pesticide in fruits followed by analysis using UV-Vis spectroscopy.

In this work, the concentrations of malathion in fruits were determined using UV-Vis spectrophotometry prior to pre-concentration using QuEChERS. The Z-sep+/PSA sorbent combination was used for the d-SPE clean-up and extraction was done using acetonitrile during QuEChERS. The absorbance of malathion was measured using a UV-Vis spectrophotometer at a wavelength of 415 nm. The QuEChERS parameters, which included type and volume of extraction solvent, type and mass of sorbents, and centrifugation rate, were optimised prior to application of the developed method to real fruit samples. The linear range was from 0.1 to 0.9 mg kg-1 while the coefficient of determination (R2) was 0.9999. The limit of detection (LOD) for malathion was found to be 0.017 mg kg-1 and the limit of quantification was 0.05 mg kg-1. Orange samples were found to have no malathion residues when the developed method was applied to them while the concentrations of malathion in apple and pear samples were 0.07 mg kg-1 and 0.09 mg kg-1 respectively.

Qualitative enzymatic detection of organophosphate and carbamate insecticides.

In this study, new polymers containing amides (TrisPS-Ntaa, and TrisPS-Ntaa-Fc) were synthesized by condensation reaction for qualitative identification of insecticides. The synthesized polymers, including amides were investigated by infrared spectroscopy (IR), scanning electron microscopy-energy dispersion X- ray spectrometry (SEM-EDX), and gel permeation chromatography (GPC). Then, acetylcholinesterase enzyme (AChE) was covalently immobilized on these polymers to improve properties (including activity, reusability, and storage stability). Accordingly, organophosphate (malathion, acephate, chlorpyrifos methyl) and carbamate (carbofuran, methiocarb, methomyl), which are used to prevent harmful organisms in some agricultural products were enzymatically determined based on their inhibitory activity on AChE.

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.