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Mikrochimica Acta May 2024In the ratiometric fluorescent (RF) strategy, the selection of fluorophores and their respective ratios helps to create visual quantitative detection of target analytes....
In the ratiometric fluorescent (RF) strategy, the selection of fluorophores and their respective ratios helps to create visual quantitative detection of target analytes. This study presents a framework for optimizing ratiometric probes, employing both two-component and three-component RF designs. For this purpose, in a two-component ratiometric nanoprobe designed for detecting methyl parathion (MP), an organophosphate pesticide, yellow-emissive thioglycolic acid-capped CdTe quantum dots (Y-QDs) (analyte-responsive), and blue-emissive carbon dots (CDs) (internal reference) were utilized. Mathematical polynomial equations modeled the emission profiles of CDs and Y-QDs in the absence of MP, as well as the emission colors of Y-QDs in the presence of MP separately. In other two-/three-component examples, the detection of dopamine hydrochloride (DA) was investigated using an RF design based on blue-emissive carbon dots (B-CDs) (internal reference) and N-acetyl L-cysteine functionalized CdTe quantum dots with red/green emission colors (R-QDs/G-QDs) (analyte-responsive). The colors of binary/ternary mixtures in the absence and presence of MP/DA were predicted using fitted equations and additive color theory. Finally, the Euclidean distance method in the normalized CIE XYZ color space calculated the distance between predicted colors, with the maximum distance defining the real-optimal concentration of fluorophores. This strategy offers a more efficient and precise method for determining optimal probe concentrations compared to a trial-and-error approach. The model's effectiveness was confirmed through experimental validation, affirming its efficacy.
PubMed: 38740592
DOI: 10.1007/s00604-024-06403-3 -
Chemosphere Apr 2024This study investigated the occurrence and seasonal distribution of different classes of pesticides in surface waters of the Ondas River Watershed, as well as potential...
This study investigated the occurrence and seasonal distribution of different classes of pesticides in surface waters of the Ondas River Watershed, as well as potential risks to the aquatic health and human water consumption in the western region of Bahia state, Brazil. Two gas chromatography-mass spectrometry analytical methods were applied to monitor 34 pesticides in water samples collected during both the dry and rainy seasons at 17 sites. Upon individual analysis, only γ-HCH, methoxychlor, demeton-S, methyl parathion, fenitrothion, chlorpyrifos, and azoxystrobin exhibited statistically significant differences between seasons. During rainy season, concentration medians of residues were higher for γ-HCH (74.7 ng L), methoxychlor (25.1 ng L), and azoxystrobin (47.2 ng L), potentially linked to historical contamination or illegal use. Conversely, pesticides like methyl parathion, fenitrothion, and chlorpyrifos, belonging to the organophosphate class, showed higher concentration medians in the dry period, measuring 75.1, 5.50, and 10.8 ng L, respectively, probably due to region crop activities. The risk quotient (RQ) assessment for aquatic life indicated that 59.0% of the samples in the dry season and 76.0% in the rainy season had RQ values greater than one, signifying a critical scenario for species conservation. Regarding human consumption, elevated risks were observed for heptachlor in both sampling periods and for azoxystrobin during the rainy season, surpassing RQ levels above 1, indicating danger in untreated water ingestion. Additionally, 24.0% and 53.0% of the samples in the dry and rainy seasons, respectively, contained at least one pesticide exceeding the EU resolution limit (100 ng L). Therefore, considering this information, implementing mitigation measures to avoid the river's contamination becomes imperative.
Topics: Humans; Pesticides; Seasons; Rivers; Brazil; Water; Hexachlorocyclohexane; Chlorpyrifos; Methyl Parathion; Methoxychlor; Fenitrothion; Water Pollutants, Chemical; Risk Assessment; Environmental Monitoring; Strobilurins; Pyrimidines
PubMed: 38490616
DOI: 10.1016/j.chemosphere.2024.141659 -
Journal of Pharmaceutical and... Aug 2024Pesticides play an important role in forensic toxicology and are usually classified as a single class of chemicals. Despite their commonly perceived unity, pesticides...
Development and validation of a multi-substance method for routine analysis of pesticides in post-mortem samples by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry.
Pesticides play an important role in forensic toxicology and are usually classified as a single class of chemicals. Despite their commonly perceived unity, pesticides encompass a spectrum of compounds, including organophosphates, carbamates, pyrethroids or organochlorines, among others, each with varying degrees of toxicity. Pesticide analysis in post-mortem samples can be difficult due to the complexity of the samples and to the high toxicity of these compounds. The aim of this study was to develop and validate an easy to use, sensitive, and robust method, using ultra-performance liquid chromatography-tandem mass spectrometry to be incorporated in the routine flow for pesticide analysis in post-mortem blood samples. Described herein is a streamlined, expeditious, yet highly efficient method facilitating the screening, qualitative assessment, and quantitative confirmation of 15 pesticides, including acetamiprid, azinphos-ethyl, bendiocarb, carbofuran, chlorfenvinphos, dimethoate, imidaclopride, malathion, methiocarb, methomyl, parathion, pirimicarb, strychnine, tetrachlorvinphos, and thiacloprid in post-mortem blood, recognizing the pivotal role blood plays in forensic investigations. The developed method was linear from 10 to 200 ng/mL; limits of detection were between 1 and 10 ng/mL, depending on the compound; it was successfully evaluated a dilution ratio of 1-2, 5 and 10; and 8 substances showed maximum stability for the time interval studied. This UHPLC-MS/MS method is useful and a powerful tool in a toxicology lab because it is fast, simple, effective, and trustworthy. The results of this validation highlight the robustness of the analytical method, providing a valuable tool for the accurate and sensitive detection of pesticides in post-mortem blood. Poised for routine implementation, this method has already found success in suspected intoxication cases, promising to elevate the standards of forensic pesticide analysis.
Topics: Tandem Mass Spectrometry; Chromatography, High Pressure Liquid; Humans; Pesticides; Forensic Toxicology; Reproducibility of Results; Autopsy; Limit of Detection
PubMed: 38701535
DOI: 10.1016/j.jpba.2024.116176 -
ACS Omega Dec 2023Exfoliated kaolinite nanosheets (EXK) and their hybridization with β-cyclodextrin (β-CD/EXK) were evaluated as potential-enhanced adsorbents of methyl parathion (MP)...
Advanced Equilibrium Modeling for the Synergetic Effect of β-Cyclodextrin Integration on the Adsorption Efficiency of Methyl Parathion by β-Cyclodextrin/Exfoliated Kaolinite Nanocomposite.
Exfoliated kaolinite nanosheets (EXK) and their hybridization with β-cyclodextrin (β-CD/EXK) were evaluated as potential-enhanced adsorbents of methyl parathion (MP) in synergetic investigations to determine the effects of the different modification procedures. The adsorption behaviors were described on the basis of the energetic steric and energetic factors of the specific advanced equilibrium models (monolayer model of one energy). The functionalization process with β-CD enhanced the adsorption behaviors of MP considerably to 350.6 mg/g in comparison to EXK (291.7 mg/g) and natural kaolinite (K) (244.7 mg/g). The steric studies revealed a remarkable improvement in the quantities of the existing receptors after exfoliation ( = 134.4 mg/g) followed by β-CD hybridization ( = 162.3 mg/g) as compared to K (75.7 mg/g), which was reflected in the determined adsorption capacities of MP. Additionally, each active free site of β-CD/EXK can adsorb about 3 molecules of MP, which occur in a vertical orientation by types of multimolecular mechanisms. The energetic investigations of Gaussian energy (<8.6 kJ/mol) and adsorption energy (<40 kJ/mol) validate the physical adsorption of MP, which might involve the cooperation of dipole bonding forces, van der Waals, and hydrogen bonding. The properties and entropy values, free enthalpy, and intern energy as the investigated thermodynamic functions declared the exothermic and spontaneous behaviors of the MP adsorption.
PubMed: 38144066
DOI: 10.1021/acsomega.3c07088 -
Environmental Research Feb 2024Organophosphates pesticide (OP) toxicity through water resources is a large concern globally among all the emerging pollutants. Detection of OPs is a challenge which...
Recombinant Organophosphorus acid anhydrolase (OPAA) enzyme-carbon quantum dot (CQDs)-immobilized thin film biosensors for the specific detection of Ethyl Paraoxon and Methyl Parathion in water resources.
Organophosphates pesticide (OP) toxicity through water resources is a large concern globally among all the emerging pollutants. Detection of OPs is a challenge which needs to be addressed considering the hazardous effects on the health of human beings. In the current research thin film biosensors of recombinant, Organophosphorus acid anhydrolase (OPAA) enzyme along with carbon quantum dots (CQDs) immobilized in thin films were developed. OPAA-CQDs thin film biosensors were used for the specific detection of two OPs Ethyl Paraoxon (EP) and Methyl Parathion (MP) in river water and household water supply. Recombinant OPAA enzyme was expressed in E. Coli, purified and immobilized on the CQD containing chitosan thin films. The CQDs used for this purpose were developed by a one-pot hydrothermal method from phthalic acid and Tri ethylene diamine. The properties of CQDs, OPAA and thin films were characterized using techniques like XPS, TEM, XRD, enzyme activity and CLSM measurements. Biosensing studies of EP and MP were performed by taking fluorescence measurements using a fiber optic spectrometer. The analytical parameters of biosensing were compared against an estimation carried out using the HPLC method. The biosensing performance indicates that the OPAA-CQDs thin film-based biosensors were able to detect both EP and MP in a range of 0-100 μM having a detection limit of 0.18 ppm/0.69 ppm for EP/MP, respectively with a response time of 5 min. The accuracy of estimation of EP/MP when spiked in water resources lie in the range of ∼100-102% which clearly indicates the OPAA-CQD based thin film biosensors can function as a point-of-use method for the detection of OP pesticides in complex water resources.
Topics: Humans; Paraoxon; Aryldialkylphosphatase; Methyl Parathion; Quantum Dots; Carbon; Water Resources; Escherichia coli; Pesticides; Parathion; Biosensing Techniques
PubMed: 38070850
DOI: 10.1016/j.envres.2023.117855 -
Chemosphere Jan 2024This article presents a novel and highly efficient electrocatalytic degradation method for two significant organophosphorus pesticides, fenitrothion (FEN), and methyl...
Boosted electrocatalytic oxidation of organophosphorus pesticides by a novel high-efficiency CeO-Doped PbO anode: An electrochemical study, parameter optimization and degradation mechanisms.
This article presents a novel and highly efficient electrocatalytic degradation method for two significant organophosphorus pesticides, fenitrothion (FEN), and methyl parathion (MPN), using a Ti/β-PbO-CeO modified anode (indirect oxidation). A comprehensive electrochemical investigation was also carried out to gain new insight into the redox behavior and destruction pathway of these pesticides (direct oxidation). The study also explores the effects of various operating parameters, such as initial solution pH, applied current density, and initial pesticides concentration, on the conversion-paired electrocatalytic removal process. To further enhance the degradation efficiency, a new configuration of the electrochemical cell was designed, employing two types of electrodes and two independent power supply devices. The conversion paired electrocatalytic degradation process of these pesticides involves first the direct reduction of FEN (or MPN) on a graphite cathode and then the indirect oxidation of reduced FEN (or MPN) by hydroxyl radicals electro generated on the Ti/β-PbO-CeO anode. The synergism of these two processes together will effectively lead to FEN (or MPN) degradation. The degradation percentages of 98% for FEN and 95% for MPN at the optimal conditions for the electrochemical degradation of these pesticides were achieved at pH = 7, initial concentration 50 mg L, with a current density of 90 mA cm for direct reduction and 11 mA cm for indirect oxidation. Overall, this study presents a promising and efficient approach for the remediation of organophosphorus pesticide-contaminated environments, offering valuable insights into the electrochemical degradation process and highlighting the potential for practical application in wastewater treatment and environmental protection.
Topics: Pesticides; Organophosphorus Compounds; Oxides; Oxidation-Reduction; Methyl Parathion; Electrodes; Titanium; Water Pollutants, Chemical
PubMed: 37925025
DOI: 10.1016/j.chemosphere.2023.140597 -
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 -
Food Chemistry Aug 2024The development of a robust electrocatalyst for the electrochemical sensor for hazardous pesticides will reduce its effects on the ecosystem. Herein, we synthesized the...
The development of a robust electrocatalyst for the electrochemical sensor for hazardous pesticides will reduce its effects on the ecosystem. Herein, we synthesized the robust manganese cobalt phosphide (MnCoP) - Core-shell as an electrochemical sensor for the determination of hazardous pesticide methyl parathion (MP). The MnCoP- Core-shell was prepared with the sustainable self-template route can help with the larger surface area. The Core-shell structure of MnCoP possesses a higher active surface area which increases the electrocatalytic performance and is utilized to improve the electrochemical MP reduction with the synergism of the core and shell structure. Remarkably, it realizes the higher sensitivity (0.014 μA μM cm) of MnCoP- Core-shell/GCE achieves towards MP with lower limit of detection (LoD 50 nM) and exceptional recovery rate of MP in vegetable samples are achieved with the differential pulse voltammetry (DPV) technique. The MnCoP- Core-shell electrode reserved their superior electrochemical performances with high reproducibility and repeatability. This prominent activity of the MnCoP core-shell towards the MP in real sample analysis, makes it a promising electrochemical sensor for the detection of MP.
Topics: Electrochemical Techniques; Cobalt; Methyl Parathion; Food Contamination; Manganese; Limit of Detection; Phosphines; Vegetables; Electrodes; Pesticides
PubMed: 38653046
DOI: 10.1016/j.foodchem.2024.139152 -
Journal of Environmental Management Feb 2024Food safety is an important issue of most concern for health, while pesticides are one of the main threats to food safety. In view of the potential health hazard of...
Food safety is an important issue of most concern for health, while pesticides are one of the main threats to food safety. In view of the potential health hazard of pesticides in food, the cancer and non-cancer risks were assessed for 19 kinds of pesticides in Chinese food in this study. Furthermore, the health risks of different types of pesticides were compared to uncover the most polluted pesticide types in this study. Results show that methyl parathion, dichlorvos and 2,4-D residues in some food groups exceed the Chinese food standards. The cumulative disease burden of six carcinogenic pesticides for people older than 40 years ranges from 1.03 × 10 to 2.27 × 10, which exceeds the WHO recommended limit of 10. The non-cancer risks of 13 kinds of pesticides are all lower than 1 and will not pose appreciable health risk to the consumers. Livestock and poultry (contribution rate = 38.93%) and Milk and dairy products (contribution rate = 22.38%) are the dominate risk exposure sources for carcinogenic pesticides while staple foods (contribution rate = 31.62%) and vegetables (contribution rate = 21.5%) are the main risk exposure sources for non-carcinogenic pesticides. Comparing the risks of different pesticide types, insecticide is the most harmful category in this study, followed by herbicide and acaricide. This study characterized the health risks of pesticides in Chinese food and provided a scientific basis for pesticide management.
Topics: Humans; Pesticides; Pesticide Residues; Insecticides; Vegetables; Food Contamination; Risk Assessment; Neoplasms
PubMed: 38128207
DOI: 10.1016/j.jenvman.2023.119813 -
ACS Applied Materials & Interfaces Jun 2024The catalytic efficiency of enzymes can be harnessed as an environmentally friendly solution for decontaminating various xenobiotics and toxins. However, for some...
The catalytic efficiency of enzymes can be harnessed as an environmentally friendly solution for decontaminating various xenobiotics and toxins. However, for some xenobiotics, several enzymatic steps are needed to obtain nontoxic products. Another challenge is the low durability and stability of many native enzymes in their purified form. Herein, we coupled peptide-based encapsulation of bacterial phosphotriesterase with soil-originated bacteria, sp. 4Hβ as an efficient system capable of biodegradation of paraoxon, a neurotoxin pesticide. Specifically, recombinantly expressed and purified methyl parathion hydrolase (MPH), with high hydrolytic activity toward paraoxon, was encapsulated within peptide nanofibrils, resulting in increased shelf life and retaining ∼50% activity after 132 days since purification. Next, the addition of sp. 4Hβ, capable of degrading para-nitrophenol (PNP), the hydrolysis product of paraoxon, which is still toxic, resulted in nondetectable levels of PNP. These results present an efficient one-pot system that can be further developed as an environmentally friendly solution, coupling purified enzymes and native bacteria, for pesticide bioremediation. We further suggest that this system can be tailored for different xenobiotics by encapsulating the rate-limiting key enzymes followed by their combination with environmental bacteria that can use the enzymatic step products for full degradation without the need to engineer synthetic bacteria.
PubMed: 38920304
DOI: 10.1021/acsami.4c06501