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Foods (Basel, Switzerland) Sep 2023In modern agricultural practices, organophosphorus pesticides or insecticides (OPs) are regularly used to restrain pests. Their limits are closely monitored since their...
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 R 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.
PubMed: 37685251
DOI: 10.3390/foods12173319 -
Heliyon Sep 2023Organophosphorus Pesticides () are among the extensively used pesticides throughout the world to boost agricultural production. However, persistent residues of these... (Review)
Review
Organophosphorus Pesticides () are among the extensively used pesticides throughout the world to boost agricultural production. However, persistent residues of these toxic pesticides in various vegetables, fruits, and drinking water poses detrimental health effects. Consequently, the rapid monitoring of these harmful chemicals through simple and cost-effective methods has become crucial. In such an instance, electrochemical methods offer simple, rapid, sensitive, reproducible, and affordable detection pathways. To overcome the limitations associated with electrochemical enzymatic sensors, non-enzymatic sensors have emerged as promising and simpler alternatives. The non-enzymatic sensors have demonstrated superior activity, reaching detection limit up to femto (10) molar concentration in recent years, leveraging higher selectivity obtained through the molecularly imprinted polymers, synergistic effects between carbonaceous nanomaterials and metals, metal oxide alloys, and other alternative approaches. Herein, this review paper provides an overview of the recent advancements in the development of non-enzymatic electrochemical sensors for the detection of commonly used OPPs, such as Chlorpyrifos (), Diazinon (), Malathion (), Methyl parathion () and Fenthion (). The design method of the electrodes, electrode functioning mechanism, and their analytical performance metrics, such as limit of detection, sensitivity, selectivity, and linearity range, were reviewed and compared. Furthermore, the existing challenges within this rapidly growing field were discussed along with their potential solutions which will facilitate the fabrication of advanced and sustainable non-enzymatic sensors in the future.
PubMed: 37662791
DOI: 10.1016/j.heliyon.2023.e19299 -
Proteins Jan 2024Methyl parathion hydrolase (MPH) is an enzyme of the metallo-β-lactamase superfamily, which hydrolyses a wide range of organophosphates (OPs). Recently, MPH has...
Methyl parathion hydrolase (MPH) is an enzyme of the metallo-β-lactamase superfamily, which hydrolyses a wide range of organophosphates (OPs). Recently, MPH has attracted attention as a promising enzymatic bioremediator. The crystal structure of MPH enzyme shows a dimeric form, with each subunit containing a binuclear metal ion center. MPH also demonstrates metal ion-dependent selectivity patterns. The origins of these patterns remain unclear but are linked to open questions about the more general role of metal ions in functional evolution and divergence within enzyme superfamilies. We aimed to investigate and compare the binding of different OP pesticides to MPH with cobalt(II) metal ions. In this study, MPH was modeled from Ochrobactrum sp. with different OP pesticides bound, including methyl paraoxon and dichlorvos and profenofos. The docked structures for each substrate optimized by DFT calculation were selected and subjected to atomistic molecular dynamics simulations for 500 ns. It was found that alpha metal ions did not coordinate with all the pesticides. Rather, the pesticides coordinated with less buried beta metal ions. It was also observed that the coordination of beta metal ions was perturbed to accommodate the pesticides. The binding free energy calculations and structure-based pharmacophore model revealed that all the three substrates could bind well at the active site. However, profenofos exhibit a stronger binding affinity to MPH in comparison to the other two substrates. Therefore, our findings provide molecular insight on the binding of different OP pesticides which could help us design the enzyme for OP pesticides degradation.
Topics: Methyl Parathion; Organophosphates; Hydrolases; Ochrobactrum; Phosphoric Monoester Hydrolases; Pesticides; Metals; Ions
PubMed: 37646471
DOI: 10.1002/prot.26579 -
Journal of Fluorescence Aug 2023Sensors play a critical role in the detection and monitoring of various substances present in our environment, providing us with valuable information about the world... (Review)
Review
Sensors play a critical role in the detection and monitoring of various substances present in our environment, providing us with valuable information about the world around us. Within the field of sensor development, one area that holds particular importance is the detection of small molecules. Small molecules encompass a wide range of organic or inorganic compounds with low molecular weight, typically below 900 Daltons including gases, volatile organic compounds, solvents, pesticides, drugs, biomarkers, toxins, and pollutants. The accurate and efficient detection of these small molecules has attracted significant interest from the scientific community due to its relevance in diverse fields such as environmental pollutants monitoring, medical diagnostics, industrial optimization, healthcare remedies, food safety, ecosystems, and aquatic and terrestrial life preservation. To meet the demand for precise and efficient monitoring of small molecules, this summary aims to provide an overview of recent advancements in sensing and quantification strategies for various organic small molecules including Hydrazine, Glucose, Morpholine, Ethanol amine, Nitrosamine, Oxygen, Nitro-aromatics, Phospholipids, Carbohydrates, Antibiotics, Pesticides, Drugs, Adenosine Triphosphate, Aromatic Amine, Glutathione, Hydrogen Peroxide, Acetone, Methyl Parathion, and Thiophenol. The focus is on understanding the receptor sensing mechanism, along with the electrical, optical, and electrochemical response. Additionally, the variations in UV-visible spectral properties of the ligands upon treatment with the receptor, fluorescence and absorption titration analysis for limit of detection (LOD) determination, and bioimaging analysis are discussed wherever applicable. It is anticipated that the information gathered from this literature survey will be helpful for the perusal of innovation regarding sensing strategies.
PubMed: 37644375
DOI: 10.1007/s10895-023-03387-w -
Small (Weinheim An Der Bergstrasse,... Dec 2023For the enzyme immobilization platform, enhancing enzyme activity retention while improving enzyme stability remains a challenge for sensitive sensing analysis. Herein,...
For the enzyme immobilization platform, enhancing enzyme activity retention while improving enzyme stability remains a challenge for sensitive sensing analysis. Herein, an in situ biomimetic immobilized enzyme carrier (metal-pyrimidine nanoflowers, MPNFs) synthesized by the coordination of DNA base derivative (2-aminopyrimidine) with Zn in the aqueous phase at room temperature is developed. The biocompatibility of 2-aminopyrimidine and the hydrophilicity and green synthetic conditions of MPNFs allows the immobilized enzymes to retain above 91.2% catalytic activity. On this basis, a cascade catalytic platform is constructed by simultaneously immobilizing acetylcholinesterase (AChE), choline oxidase (CHO), and horseradish peroxidase (HRP) in MPNFs (AChE/CHO/HRP@MPNFs) for organophosphorus pesticides (OPs) colorimetric biosensing detection. The assay could specifically detect parathion-methyl within 13 min with a wider linear range (0.1-1000.0 nm) and a lower limit of detection (LOD) (0.032 nm). The remarkable stability of the immobilized enzymes is also achieved under harsh environments, room temperature storage, and recycling. Furthermore, a portable and cost-effective biosensing platform is developed by integrating AChE/CHO/HRP@MPNFs with a smartphone-assisted paper device for the on-site detection of OPs. Overall, the high catalytic activity retention and the enhanced detection performance demonstrate that MPNF is a robust carrier in enzyme immobilization and holds great promise in biosensing and other field applications.
Topics: Pesticides; Acetylcholinesterase; Organophosphorus Compounds; Enzymes, Immobilized; Biomimetics; Metals; Horseradish Peroxidase; Pyrimidines; Biosensing Techniques; Colorimetry
PubMed: 37612822
DOI: 10.1002/smll.202304077 -
Environmental Monitoring and Assessment Aug 2023The recovery of organophosphate pesticides (OPPs) from aqueous solutions is imperative considering their agricultural and environmental implications. Among various...
The recovery of organophosphate pesticides (OPPs) from aqueous solutions is imperative considering their agricultural and environmental implications. Among various mitigation approaches used for OPPs' removal, adsorption offers many advantageous features for OPPs abatement owing to its benign nature, cost-effective processing, and non-requirement of excessive equipment. This research describes the adsorptive removal of three organophosphate pesticides (OPPs) namely chlorpyrifos (CPF), methyl parathion (MP), and malathion (MAL) by HKUST-1 (HKUST = Hong Kong University of Science and Technology) metal-organic framework (MOF). The synthesis of HKUST-1 MOFs was confirmed by various spectroscopic and microscopic techniques. The adsorption kinetics was systematically investigated by varying three parameters to include solution pH, contact time, and initial pesticide concentration. Among all the three pesticides, HKUST-1 showed enhanced removal of CPF in terms of pH, resulting in an adsorption capacity of 1.82 mg·g. However, under the effect of contact time at 60 min, the adsorption capacity of HKUST-1 for PM, MAL, and CPF were computed to be 1.83, 1.79, and 0.44 mg·g, respectively. Besides, HKUST-1 showed a remarkable performance towards adsorptive removal of MAL (14.01 mg·g at 10 mg·L concentration) with linear increase in adsorption capacity as the function of initial pesticide concentration. The MOFs were also able to retain ca. 50% of their adsorption efficiency over the course of five cycles of adsorptive removal of CP. In the future, a comprehensive data table showing the performance of various MOFs against various OPPs can be constructed on the basis of parameters used in this study.
Topics: Metal-Organic Frameworks; Adsorption; Environmental Monitoring; Insecticides; Chlorpyrifos; Malathion; Pesticides; Organophosphorus Compounds
PubMed: 37592149
DOI: 10.1007/s10661-023-11662-3 -
Sheng Wu Gong Cheng Xue Bao = Chinese... Jul 2023The evaluation of the bioavailability of pollutants in soil is crucial to accurately assess the pollution risk, and whole-cell biosensor is one of the important tools...
The evaluation of the bioavailability of pollutants in soil is crucial to accurately assess the pollution risk, and whole-cell biosensor is one of the important tools for such evaluation. This study aimed to develop a novel whole-cell biosensor for the detection of methyl parathion in soil using. First, a whole-cell biosensor was constructed by the screened methyl parathion hydrolase gene, the existing specific induction element R, and the pUC19 plasmid skeleton. Then, the detection method of methyl parathion in soil extracts was established using 96-well microtiter plate as carrier and five whole-cell biosensors as indicator. The method was applied in the detection of methyl parathion in tested and field soil extracts. Taking . DH5α/pMP-AmilCP with the best detection performance as an example, this biosensor had a detection limit of 6.21-6.66 µg/L and a linear range of 10-10 000 µg/L for methyl parathion in four soil extracts. . DH5α/pMP-RFP and . DH5α/pMP-AmilCP methods have good detection performance for the analysis of methyl parathion in soil extract samples. This biosensor method can help to quickly assess the bioavailability of methyl parathion in soil, and thus help to understand the risk of soil pollution caused by organophosphorus pesticide methyl parathion.
Topics: Methyl Parathion; Pesticides; Organophosphorus Compounds; Escherichia coli; Soil; Farms; Biosensing Techniques
PubMed: 37584126
DOI: 10.13345/j.cjb.230129 -
Foods (Basel, Switzerland) Aug 2023In this study, a colorimetric sensor was developed for the detection of organophosphorus pesticides (OPs) using a heterogeneous nanozyme with phosphatase-like activity....
In this study, a colorimetric sensor was developed for the detection of organophosphorus pesticides (OPs) using a heterogeneous nanozyme with phosphatase-like activity. Herein, this heterogeneous nanozyme (Au-pCeO) was obtained by the modification of gold nanoparticles on porous cerium oxide nanorods, resulting in synergistic hydrolysis performance for OPs. Taking methyl parathion (MP) as the target pesticide, the catalytic performance and mechanism of Au-pCeO were investigated. Based on the phosphatase-like Au-pCeO, a dual-mode colorimetric sensor for MP was put forward by the analysis of the hydrolysis product via a UV-visible spectrophotometer and a smartphone. Under optimum conditions, this dual-mode strategy can be used for the on-site analysis of MP with concentrations of 5 to 200 μM. Additionally, it can be applied for MP detection in pear and lettuce samples with recoveries ranging from 85.27% to 115.87% and relative standard deviations (RSDs) not exceeding 6.20%, which can provide a simple and convenient method for OP detection in agricultural products.
PubMed: 37569249
DOI: 10.3390/foods12152980 -
Food Chemistry Jan 2024A thermosensitive magnetic-molecularly-imprinted polymer (TMMIP) was successfully prepared in an aqueous medium. The TMMIP was applied as an effective adsorbent in...
Eco-friendly thermosensitive magnetic-molecularly-imprinted polymer adsorbent in dispersive solid-phase microextraction for gas chromatographic determination of organophosphorus pesticides in fruit samples.
A thermosensitive magnetic-molecularly-imprinted polymer (TMMIP) was successfully prepared in an aqueous medium. The TMMIP was applied as an effective adsorbent in dispersive solid-phase microextraction for the selective enrichment of five organophosphorus pesticides (OPPs; diazinon, fenitrothion, fenthion, parathion-ethyl, and ethion) before analysis by gas chromatography. The polymerization was performed using mixed-valence iron hydroxide nanoparticles as the magnetic support, N-isopropyl acrylamide as the thermosensitive monomer, ethion as the template, and methacrylic acid as the functional monomer. The adsorption and desorption mechanisms of OPPs depend on their interactions with the adsorbents and solution temperature. Our methodology provides good linearity (0.50-2000 µgL), with a correlation determination of R > 0.9980, low limit of detection (0.25-0.50 µgL), low limit of quantitation (0.50-1.50 μg L), and high precision (%RSD < 7%). The developed method demonstrates excellent applicability for accurately and efficiently determining OPP residuals in fruit and vegetable samples with good recoveries (93-117%).
Topics: Pesticides; Fruit; Organophosphorus Compounds; Molecularly Imprinted Polymers; Chromatography, Gas; Magnetic Phenomena; Limit of Detection; Solid Phase Extraction
PubMed: 37562262
DOI: 10.1016/j.foodchem.2023.137069 -
Archives of Environmental Contamination... Oct 2023Pesticide residues are regularly found in surface water, which could be dangerous for freshwater ecosystems and biodiversity. Pesticides may enter waters through a...
Pesticide residues are regularly found in surface water, which could be dangerous for freshwater ecosystems and biodiversity. Pesticides may enter waters through a variety of pathways, but runoff from irrigation or precipitation has the highest quantities. Previous studies analyzing the pesticides pollution or ecological risks of pesticides focused on few regions (e.g., European and United States), whereas analysis of pesticide pollution in Southeast Asia and especially in Vietnam is limited. This study presents an investigation of banned pesticides used across the range of land use in catchments of the Ma river and its tributaries in Thanh Hoa province, Vietnam. Applying principal component analysis (PCA), we investigated the relationship between specific pesticides and land use. Besides, cluster analysis (CA), the method of aggregating monitoring locations, was applied in this study to find spatial pattern of pesticides pollution. Due to their persistence and remobilization during floods and runoff, all ten banned pesticides-eight insecticides (aldrin/dieldrin, BHC, chlordane, endrin, heptachlor, lindane, malathion, and parathion) and two herbicides (paraquat, and 2,4D)-still remain in surface water and are not presumably influenced by the fraction of land use area in the catchments. Clustering results revealed that banned pesticides still occur in some areas. Site TH08 close to Le Mon industrial zone and TH18 in Thanh Hoa city have higher concentrations of banned pesticides than other sites due to their highly toxic and long-time existence in the environment. Overall, our study provides approach to investigate pesticides in surface water for a province in Vietnam that may be used for future ecotoxicological studies to enhance risk assessment for stream ecosystems.
Topics: Pesticides; Rivers; Vietnam; Water; Ecosystem; Water Pollutants, Chemical; Environmental Monitoring
PubMed: 37515646
DOI: 10.1007/s00244-023-01018-w