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Biosensors Feb 2023Analytical methods for detecting neurotransmitters (NTs) and organophosphorus (OP) pesticides with high sensitivity are vitally necessary for the rapid identification of...
Analytical methods for detecting neurotransmitters (NTs) and organophosphorus (OP) pesticides with high sensitivity are vitally necessary for the rapid identification of physical, mental, and neurological illnesses, as well as to ensure food safety and safeguard ecosystems. In this work, we developed a supramolecular self-assembled system (SupraZyme) that exhibits multi-enzymatic activity. SupraZyme possesses the ability to show both oxidase and peroxidase-like activity, which has been employed for biosensing. The peroxidase-like activity was used for the detection of catecholamine NTs, epinephrine (EP), and norepinephrine (NE) with a detection limit of 6.3 µM and 1.8 µM, respectively, while the oxidase-like activity was utilized for the detection of organophosphate pesticides. The detection strategy for OP chemicals was based on the inhibition of acetylcholine esterase (AChE) activity: a key enzyme that is responsible for the hydrolysis of acetylthiocholine (ATCh). The corresponding limit of detection of paraoxon-methyl (POM) and methamidophos (MAP) was measured to be 0.48 ppb and 15.8 ppb, respectively. Overall, we report an efficient supramolecular system with multiple enzyme-like activities that provide a versatile toolbox for the construction of sensing platforms for the colorimetric point-of-care detection of both NTs and OP pesticides.
Topics: Pesticides; Organophosphorus Compounds; Colorimetry; Ecosystem; Acetylcholinesterase; Oxidoreductases; Metals; Biosensing Techniques; Peroxidases
PubMed: 36832043
DOI: 10.3390/bios13020277 -
Environmental Science and Pollution... Apr 2023Pesticides use increased worldwide with a record in Brazil. Although several works addressed the effects of pesticides on living organisms, only a few considered their...
Pesticides use increased worldwide with a record in Brazil. Although several works addressed the effects of pesticides on living organisms, only a few considered their mixture, and even fewer tried to unravel their role in tumoral progression. Due to the relevance of cancer, in the present study, the effects of the mixture of pesticides widely used in Brazil (Glyphosate, 2,4-dichlorophenoxyacetic acid, Mancozeb, Atrazine, Acephate, and Paraquat) and their main metabolites (Aminomethylphosphonic Acid, 2,4-diclorophenol, Ethylenethiourea, Desethylatrazine, Methamidophos, and Paraquat) were investigated on the malignancy phenotype of murine melanoma B16-F1 cells after acute (24 h) and chronic (15 days) exposures. The tested concentrations were based on the Acceptable Daily Intake (ADI) value established by Brazilian legislation. The set of results showed that these chemicals modulate important parameters of tumor progression, affecting the expression of genes related to tumor aggressiveness (Mmp14 and Cd44) and multidrug resistance (Abcb1, Abcc1, and Abcc4), as well as tissue inhibitors of metalloproteinases (Timp1, Timp2, and Timp3). These findings revealed an absence of cytotoxicity but showed modulation of migration, invasion, and colonization capacity of B16-F1 cells. Together, the results point to some negative ways that exposure to pesticides can affect the progression of melanoma and raise a concern related to the increasing trend in pesticide use in Brazil, as the country is one of the major world food suppliers.
Topics: Animals; Mice; Pesticides; Paraquat; Melanoma; Phenotype; Complex Mixtures
PubMed: 36738412
DOI: 10.1007/s11356-023-25603-7 -
Journal of Agricultural and Food... Feb 2023Transition-metal oxides (TMOs) with a hollow multishelled structure have emerged as highly potential materials for high-performance electrochemical sensing, benefiting...
Oriented Design of Transition-Metal-Oxide Hollow Multishelled Micropolyhedron Derived from Bimetal-Organic Frameworks for the Electrochemical Detection of Multipesticide Residues.
Transition-metal oxides (TMOs) with a hollow multishelled structure have emerged as highly potential materials for high-performance electrochemical sensing, benefiting from their superior electronic conductivity, exceptionally large specific surface area, excellent stability, and electrochemistry properties. In particular, binary TMOs are expected to outperform unitary TMOs due to the synergistic effect of the different metals. Herein, MnCoO hollow quadruple-shelled porous micropolyhedrons (MnCoO HoQS-MPs) were prepared and employed to construct an ultrasensitive sensing platform for a multipesticide assay. Profiting from complex hollow interior structures and abundant active sites, the MnCoO HoQS-MPs manifest outstanding electrochemical properties as electrode materials for the pesticide assay. The MnCoO HoQS-MP-based biosensor demonstrated remarkable performance for monocrotophos, methamidophos, and carbaryl detection, with wide linear ranges, as well as low detection limits. This work unveils a new pathway for the ultrasensitive detection of pesticides and demonstrates tremendous potential for detecting other environmentally deleterious chemicals.
Topics: Oxides; Nitrosourea Compounds; Metals; Pesticides
PubMed: 36715487
DOI: 10.1021/acs.jafc.2c08818 -
The Science of the Total Environment Mar 2023Pesticide exposure has consistently been associated with Parkinson's disease (PD) onset. Yet, fewer epidemiologic studies have examined whether pesticides influence PD...
BACKGROUND
Pesticide exposure has consistently been associated with Parkinson's disease (PD) onset. Yet, fewer epidemiologic studies have examined whether pesticides influence PD motor and non-motor symptom progression.
OBJECTIVES
Using a geographic information system tool that integrates agricultural pesticide use reports and land use records to derive ambient exposures at residences and workplaces, we assessed associations between specific pesticides previously related to PD onset with PD symptom progression in two PD patient cohorts living in agricultural regions of California.
METHODS
We calculated the pounds of pesticide applied agriculturally near each participant's residential or occupational addresses from 1974 to the year of PD diagnosis, using a geographic information system tool that links the California Pesticide Use Reports database to land use data. We examined 53 pesticides selected a priori as they have previously been associated with PD onset. We longitudinally followed two PD patient cohorts (PEG1 N = 242, PEG2 N = 259) for an average of 5.0 years (SD ± 3.5) and 2.7 years (SD ± 1.6) respectively and assessed PD symptoms using the movement disorder specialist-administered Unified Parkinson's disease Rating Scale part III (UPDRS), Mini-Mental State Examination (MMSE), and Geriatric Depression Scale (GDS). Weighted time-to-event regression models were implemented to estimate effects.
RESULTS
Ten agricultural pesticides, including copper sulfate (pentahydrate), 2-methyl-4-chlorophenoxyacetic acid (MCPA) dimethylamine salt, tribufos, sodium cacodylate, methamidophos, ethephon, propargite, bromoxynil octanoate, monosodium methanearsonate (MSMA), and dicamba, were associated with faster symptom progression. Among these pesticides, residential or workplace proximity to higher amounts of copper sulfate (pentahydrate) and MCPA (dimethylamine salt) was associated with all three progression endpoints (copper sulfate: HRs = 1.22-1.36, 95 % CIs = 1.03-1.73; MCPA: HRs = 1.27-1.35, 95 % CIs = 1.02-1.70).
CONCLUSIONS
Our findings suggest that pesticide exposure may not only be relevant for PD onset but also PD progression phenotypes. We have implicated ten specific pesticide active ingredients in faster PD motor and non-motor decline.
Topics: Humans; Parkinson Disease; Pesticides; Copper Sulfate; 2-Methyl-4-chlorophenoxyacetic Acid; Workplace; California
PubMed: 36526213
DOI: 10.1016/j.scitotenv.2022.160851 -
Frontiers in Bioengineering and... 2022O-Acetylhomoserine (OAH) is an important platform chemical for the synthesis of L-methamidophos and l-methionine. It has been produced efficiently in . However, a wider...
O-Acetylhomoserine (OAH) is an important platform chemical for the synthesis of L-methamidophos and l-methionine. It has been produced efficiently in . However, a wider range of key factors had not been identified, limiting further increases in OAH production. This study successfully identified some limiting factors and regulated them to improve OAH titer. Firstly, an efficient clustered regularly interspaced short palindromic repeats/dead CRISPR associated protein 9 (CRISPR-dCas9) system was constructed and used to identify the key genes in central metabolism and branch pathways associated with OAH biosynthesis. Then, the gene involved in TCA cycle was identified as the most critical gene. A sequential promoter P, which showed different transcriptional intensity in different strain growth periods, was used to control the expression of gene, resulting in OAH production of 7.0 g/L at 48 h. Finally, the OAH titer of the engineered strain reached 25.9 g/L at 72 h in a 5-L bioreactor. These results show that the identification and regulation of key genes are critical for OAH biosynthesis, which would provide a better research basis for the industrial production of OAH in .
PubMed: 36185436
DOI: 10.3389/fbioe.2022.978686 -
Chemical Research in Toxicology Sep 2022Exposure to organophosphorus pesticides (OP) can have chronic adverse effects that are independent of inhibition of acetylcholinesterase, the classic target for acute OP...
Exposure to organophosphorus pesticides (OP) can have chronic adverse effects that are independent of inhibition of acetylcholinesterase, the classic target for acute OP toxicity. In pure proteins, the organophosphorus pesticide chlorpyrifos oxon induces a cross-link between lysine and glutamate (or aspartate) with loss of water. Tubulin is particularly sensitive to OP-induced cross-linking. Our goal was to explore OP-induced cross-linking in a complex protein sample, MAP-rich tubulin from and to test 8 OP for their capacity to promote isopeptide cross-linking. We treated 100 μg of MAP-rich tubulin with 100 μM chlorpyrifos, chlorpyrifos oxon, methamidophos, paraoxon, diazinon, diazoxon, monocrotophos, or dichlorvos. Each sample was separated using sodium dodecyl sulfate-polyacrylamide gel electrophoresis and stained with Coomassie blue. Five gel slices (at about 30, 50, 150, and 300 kDa, and the top of the separating gel) were removed from the lanes for each of the eight OP samples and from untreated control lanes. These gel slices were subjected to in-gel trypsin digestion. MSMS fragmentation spectra of the tryptic peptides were examined for isopeptide cross-links. Sixteen spectra yielded convincing evidence for isopeptide cross-linked peptides. Ten were from the chlorpyrifos oxon reaction, 1 from dichlorvos, 1 from paraoxon, 1 from diazinon, and 3 from diazoxon. It was concluded that catalysis of protein cross-linking is a general property of organophosphorus pesticides and pesticide metabolites. Data are available via ProteomeXchange with identifier PXD034529.
Topics: Acetylcholinesterase; Aspartic Acid; Chlorpyrifos; Diazinon; Dichlorvos; Glutamates; Lysine; Monocrotophos; Organophosphorus Compounds; Paraoxon; Peptides; Pesticides; Sodium Dodecyl Sulfate; Trypsin; Tubulin; Water
PubMed: 36048166
DOI: 10.1021/acs.chemrestox.2c00194 -
RSC Advances Apr 2022A colloidal silver nanoparticle (AgNP)-based lateral flow immunoassay (LFIA) was evaluated in terms of the rapid detection of profenofos (PEO) pesticide residue in...
A colloidal silver nanoparticle (AgNP)-based lateral flow immunoassay (LFIA) was evaluated in terms of the rapid detection of profenofos (PEO) pesticide residue in vegetables. Colloidal AgNPs, of a diameter of approximately 20 nm, were surface-modified with trisodium citrate dehydrate (TSC) in order to improve their stability and dispersion. An anti-profenofos polyclonal antibody (pAb) was successfully immobilized on the surface of the AgNPs by ionic interaction and characterized using UV-vis, SEM, TEM, FTIR and XPS analyses. Surface modification of Ag-pAb conjugates of varying pH, pAb content and cross-reactivity was employed to design and prepare labels for use in an LFIA to examine whether these factors affect the performance of the assay. The visible detection limit and optical detection limit of the PEO test strip were 0.20 and 0.01 ppm, respectively, in PEO standard solution. This assay showed no cross-reaction with omethoate, methamidophos or pyraclofos. Finally, the PEO test strip was effectively applied for the detection of PEO in liquid vegetables A and B, with optical detection limits of 0.09 and 0.075 ppm, respectively.
PubMed: 35497005
DOI: 10.1039/d2ra01654k -
Food Chemistry Sep 2022Rapid detection of pesticide residues based on enzyme mimics has recently attracted much interest. However, most nanozymes have low activity. Herein, a "single-atom...
Rapid detection of pesticide residues based on enzyme mimics has recently attracted much interest. However, most nanozymes have low activity. Herein, a "single-atom Ce-N-C nanozyme" (SACe-N-C nanozyme) was rationally devised and verified to mimic peroxidase (POD-like) with superior activity. Based on its high POD-like activities and cascaded catalytic reactions with acetylcholinesterase (AChE), we constructed a bioactive paper for the detection of pesticide residues, which offered a portable approach to monitor fruits and vegetables within 30 min. More importantly, a 3D printed platform was integrated on the basis of SACe-N-C bioactive paper to achieve on-site portable testing of omethoate, methamidophos, carbofuran, and carbosulfan, showing limits of detection (LODs) of 55.83, 71.51, 81.81, and 74.98 ng/mL, respectively. The recovery rates were 84.09-104.68%. This study provided new insight into the design of novel single-atom nanozymes for cascaded catalytic detection and other rapid detection applications with high efficiency and low cost.
Topics: Acetylcholinesterase; Carbamates; Peroxidase; Pesticide Residues; Printing, Three-Dimensional
PubMed: 35421648
DOI: 10.1016/j.foodchem.2022.132896 -
Journal of Separation Science May 2022Acephate is widely used in crops as racemate. However, the enantioselective dissipation of acephate enantiomers has not been investigated in pakchoi. A sensitive and...
Acephate is widely used in crops as racemate. However, the enantioselective dissipation of acephate enantiomers has not been investigated in pakchoi. A sensitive and effective approach was established for determining residues of acephate and its highly toxic metabolite methamidophos enantiomers by supercritical fluid chromatography tandem mass spectrometry. Baseline separations for their enantiomers were achieved by using a Chiralcel OD-H column. The optimal chromatographic conditions were obtained as follows: CO /ethanol (95/5) as mobile phase; flow rate, 3.0 mL/min; column temperature, 40°C. The mean recoveries (RSDs) of analytes were in the range of 77-83.1% (6.1-9.9%), 75.4-87.5% (9.3-13.2%), and 81.5-84.2% (7.1-13.4%) at three fortification levels (0.005, 0.05, and 0.5 mg/kg for each enantiomer) for interday assay (n = 18). The method was used to evaluate the enantioselective dissipation of acephate and methamidophos in pakchoi. S-acephate dissipated faster than R-acephate, while the concentration of R-methamidophos was higher than that of S-methamidophos during the entire study period. The results indicated that the R-enantiomer of acephate and methamidophos was preferentially enriched in pakchoi. The established analysis approach and the study data provided useful information for the rational use of acephate in agriculture.
Topics: Chromatography, Supercritical Fluid; Insecticides; Organothiophosphorus Compounds; Phosphoramides; Stereoisomerism; Tandem Mass Spectrometry
PubMed: 35261148
DOI: 10.1002/jssc.202200006 -
Analytical Methods : Advancing Methods... Feb 2022Herein, an ionic-liquid-based effervescence-enhanced magnetic solid-phase extraction (ILE-MSPE) approach for the extraction/concentration of organophosphorus pesticides...
Herein, an ionic-liquid-based effervescence-enhanced magnetic solid-phase extraction (ILE-MSPE) approach for the extraction/concentration of organophosphorus pesticides in waters is reported with high stability and portability for rapid sample pretreatment in the field. The ionic-liquid-based magnetic effervescent tablet, composed of magnetic nanoparticles (FeO), sodium carbonate (NaCO) as an alkaline source, and an ionic liquid ([CMIM][PF]), played triple functions: extractant, dispersant, and retrieving agent. Based on the one-factor-at-a-time method, the important variables for the ILE-MSPE approach were optimized as follows: as an extractant, 70 μL of [CMIM][PF]; molar ratio of alkaline to acidic sources (NaCO : HCHO) as 1 : 1; and mass of magnetic nanoparticles (MNPs) of 30 mg. By integrating HPLC-DAD detection, the ILE-MSPE approach offered the limits of detection of 0.14-0.22 μg L and fortified recoveries of 81.4-97.6% for three representative species (methamidophos, phoxim, and parathion) in water samples. The relative standard deviations were lower than 4.9% for both the intra-day and inter-day precision. Overall, the newly developed method is environmentally benign, time-saving, and feasible for outdoor application.
Topics: Ionic Liquids; Magnetic Phenomena; Organophosphorus Compounds; Pesticides; Solid Phase Extraction; Water
PubMed: 35084403
DOI: 10.1039/d1ay01698a