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Spectrochimica Acta. Part A, Molecular... Aug 2019Development of simple and rapid methods for identification of pesticides, due to their broad usage and harmful effects on mammals, has been known as a critical demand....
Development of simple and rapid methods for identification of pesticides, due to their broad usage and harmful effects on mammals, has been known as a critical demand. Herein, we have introduced a silver nanoparticle (AgNP) based colorimetric sensor array for simultaneous identification of Azinphosmethyl (AM) and Phosalone (PS) pesticides. In the presence of the target pesticides, unmodified AgNPs at various pHs (4.5, 5.5 and 9.5) showed different aggregation behaviors. As a result of aggregation, the color and UV-Vis spectra of AgNPs changed differentially, leading to distinct response patterns for AM and PS. The aggregation induced spectral changes of AgNPs, were used to identify AM and PS with the help of linear discriminant analysis (LDA). The applicability of the proposed sensor array was then evaluated by identifying the target pesticides in apple samples. Altogether, the developed AgNPs based colorimetric sensor array can be potentially exploited as an efficient discrimination tool in the near future for agrichemical applications.
Topics: Azinphosmethyl; Colorimetry; Food Contamination; Hydrogen-Ion Concentration; Malus; Metal Nanoparticles; Organothiophosphorus Compounds; Pesticides; Silver
PubMed: 31077953
DOI: 10.1016/j.saa.2019.04.074 -
Chemosphere Oct 2023The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land...
The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land use have been associated to water pollution problems, including the emission of untreated urban wastewater and pesticides. Here we provide the first report on the influence of urbanization and intensive agriculture expansion on water quality parameters, pesticide contamination and the ecological status of Amazonian freshwater ecosystems of Ecuador. We monitored 19 water quality parameters, 27 pesticides, and the macroinvertebrate community in 40 sampling locations of the Napo River basin (northern Ecuador), including a nature conservation reserve and sites in areas influenced by African palm oil production, corn production and urbanization. The ecological risks of pesticides were assessed using a probabilistic approach based on species sensitivity distributions. The results of our study show that urban areas and areas dominated by African palm oil production have a significant influence on water quality parameters, affecting macroinvertebrate communities and biomonitoring indices. Pesticide residues were detected in all sampling sites, with carbendazim, azoxystrobin, diazinon, propiconazole and imidacloprid showing the largest prevalence (>80% of the samples). We found a significant effect of land use on water pesticide contamination, with residues of organophosphate insecticides correlating with African palm oil production and some fungicides with urban areas. The pesticide risk assessment indicated organophosphate insecticides (ethion, chlorpyrifos, azinphos-methyl, profenofos and prothiophos) and imidacloprid as the compounds posing the largest ecotoxicological hazard, with pesticide mixtures potentially affecting up to 26-29% of aquatic species. Ecological risks of organophosphate insecticides were more likely to occur in rivers surrounded by African palm oil plantations, while imidacloprid risks were identified in corn crop areas as well as in natural areas. Future investigations are needed to clarify the sources of imidacloprid contamination and to assess its effects for Amazonian freshwater ecosystems.
Topics: Pesticides; Ecuador; Insecticides; Water Quality; Ecosystem; Palm Oil; Urbanization; Environmental Monitoring; Water Pollutants, Chemical; Agriculture; Fresh Water; Rivers; Chlorpyrifos
PubMed: 37379974
DOI: 10.1016/j.chemosphere.2023.139286 -
Scientific Reports Oct 2022Transcriptional analysis of the network of transcription regulators and target pathways in exposed organisms may be a hard task when their genome remains unknown. The...
Transcriptional analysis of the network of transcription regulators and target pathways in exposed organisms may be a hard task when their genome remains unknown. The development of hundreds of qPCR assays, including primer design and normalization of the results with the appropriate housekeeping genes, seems an unreachable task. Alternatively, we took advantage of a whole transcriptome study on Rhinella arenarum larvae exposed to the organophosphorus pesticides azinphos-methyl and chlorpyrifos to evaluate the transcriptional effects on a priori selected groups of genes. This approach allowed us to evaluate the effects on hypothesis-selected pathways such as target esterases, detoxifying enzymes, polyamine metabolism and signaling, and regulatory pathways modulating them. We could then compare the responses at the transcriptional level with previously described effects at the enzymatic or metabolic levels to obtain global insight into toxicity-response mechanisms. The effects of both pesticides on the transcript levels of these pathways could be considered moderate, while chlorpyrifos-induced responses were more potent and earlier than those elicited by azinphos-methyl. Finally, we inferred a prevailing downregulation effect of pesticides on signaling pathways and transcription factor transcripts encoding products that modulate/control the polyamine and antioxidant response pathways. We also tested and selected potential housekeeping genes based on those reported for other species. These results allow us to conduct future confirmatory studies on pesticide modulation of gene expression in toad larvae.
Topics: Animals; Azinphosmethyl; Chlorpyrifos; Pesticides; Larva; Transcriptome; Organophosphorus Compounds; Antioxidants; Bufo arenarum; Esterases; Polyamines; Transcription Factors
PubMed: 36271284
DOI: 10.1038/s41598-022-21748-6 -
Dalton Transactions (Cambridge, England... Dec 2023The lanthanide metal organic framework compounds [Ln(BPTA)(Bpy)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1a-5a) and [Ln(BPTA)(Phen)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1b-5b)...
The lanthanide metal organic framework compounds [Ln(BPTA)(Bpy)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1a-5a) and [Ln(BPTA)(Phen)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1b-5b) were prepared by employing 2,5-bis(prop-2-yn-1-yloxy)terephthalic acid (2,5-BPTA) as the primary ligand and 2,2'-bipyridine (1a-5a) and 1,10-phenanthroline (1b-5b) as the secondary ligands. Single-crystal structural studies on [Gd(BPTA)(Bpy)]·0.5DMF (3a) and [Dy(BPTA)(Phen)]·0.5DMF (5b) indicated that the compounds have a two-dimensional structure. The Y compound exhibits blue emission, and the other compounds exhibit emission in the expected regions ( = 350 nm). White light emission was achieved by careful mixing of the red (Eu) and green (Tb) components in the blue emitting Y compound. Thus, YTbEu (bpy) and YTbEu (phen) were found to show white emission when excited using a wavelength of 350 nm. The introduction of N-N-containing ancillary ligands (, bpy and phen) increased the overall quantum yield (QY) of white light emission to 31% and 43%, respectively. The high QY observed for the Tb and Eu compounds was found to be sensitive and selective for the fluorometric detection of azinphos-methyl pesticide and trinitrophenol (TNP) in an aqueous medium at the ppb level. The same behaviour was observed when utilising the compounds as onsite paper strip sensors. Their magnetic properties were also studied, revealing for the Tb and Dy derivatives slow relaxation of the magnetisation at low temperature. The present study highlights the usefulness of rigid π-conjugated molecules such as 2,2'-bipyridine and 1,10-phenanthroline in enhancing the many utilities of rare-earth-containing MOFs towards white light emission, the sensing of harmful and dangerous substances and magnetic properties.
PubMed: 38013491
DOI: 10.1039/d3dt01882b -
Pesticide Biochemistry and Physiology Feb 2020The organophosphorus pesticides azinphos-methyl (AZM) and chlorpyrifos (CPF) exert their toxic action by inhibition of acetylcholinesterase, but non-target processes...
Differential effects of azinphos-methyl and chlorpyrifos on polyamine oxidative metabolism during the embryonic development of Rhinella arenarum and its relation to oxidative stress.
The organophosphorus pesticides azinphos-methyl (AZM) and chlorpyrifos (CPF) exert their toxic action by inhibition of acetylcholinesterase, but non-target processes such as polyamine metabolism can also be affected. Our objective was to evaluate the effects of different concentrations of AZM (0.5-, 2- and 9 mg L) and CPF (0.5- and 1 mg L) on polyamine oxidative metabolism along Rhinella arenarum embryonic development and to explore its relationship to oxidative stress. Free and conjugated polyamines were measured by HPLC. The activity of spermine oxidase (SMOX), N-acetylpolyamine oxidase (PAOX) and diamine oxidase (DAO) were measured through kinetic spectrofluorometry. Free putrescine and spermine were significantly increased in open mouth embryos exposed to AZM. Free polyamine levels were not affected by CPF exposure. In embryos exposed to AZM, DAO was increased in tail bud stage and SMOX was increased in open mouth stage, while embryos exposed to CPF showed an increase of PAOX activity in tail bud stage and a decrease of DAO and SMOX activity in open mouth stage. Polyamine levels and oxidative degradation enzymes respond differently if R. arenarum embryos are exposed to AZM or CPF, despite that both insecticides belong to the same chemical family. The early increase of DAO and PAOX would play a protective role to guarantee the normal progression of embryonic development. The increased production of reactive species might contribute to an oxidative stress situation generated by exposure to the insecticides and to the alteration of the antioxidant defense system. In tail bud stage embryos, PAOX and SMOX were positively correlated to acetylcholinesterase activity and reduced glutathione levels (GSH), and negatively correlated to the antioxidant enzymes catalase (CAT) and glutathione S-transferase (GST). In complete operculum embryos, a negative correlation between antioxidant parameters and polyamine levels and polyamine oxidative metabolism was observed, except for SMOX, which showed a low positive correlation with CAT and GSH and a negative correlation to PAOX and DAO. We suggest the use of DAO and PAOX as biomarkers of exposure to AZM and CPF, respectively, as they respond earlier than the classical biomarker acetylcholinesterase.
Topics: Azinphosmethyl; Chlorpyrifos; Embryonic Development; Oxidative Stress; Polyamines
PubMed: 31973851
DOI: 10.1016/j.pestbp.2019.10.007 -
Environmental Science and Pollution... Aug 2022In this study, we examined the dose-dependent effects of an environmentally relevant pesticide cocktail (metalachlor, linuron, isoproturon, tebucanazole, aclonifen,...
Potential mechanisms of Na/K-ATPase attenuation by heat and pesticides co-exposure in goldfish: role of cellular apoptosis, oxidative/nitrative stress, and antioxidants in gills.
In this study, we examined the dose-dependent effects of an environmentally relevant pesticide cocktail (metalachlor, linuron, isoproturon, tebucanazole, aclonifen, atrazine, pendimethalin, and azinphos-methyl) and temperature change (22 vs. 32 °C for 4-week exposure) on Na/K-ATPase, 3-nitrotyrosine protein (NTP), dinitrophenyl protein (DNP), catalase (CAT), and superoxide dismutase (SOD) expressions in gills of goldfish (Carassius auratus). Histopathological analysis showed widespread damage to gill in elevated temperature (32 °C) and pesticide co-exposure groups, including fusion of secondary lamellae, club-shaped primary lamellae, rupture of epithelial layer, loss of normal architecture, and hemorrhaging. Immunohistochemical and qRT-PCR analyses showed significant decreases in Na/K-ATPase protein and mRNA expressions in gills exposed to higher temperature and pesticides; however, combined exposure to heat and pesticides significantly increases NTP, DNP, CAT, and SOD expressions. In situ TUNEL assay revealed elevated levels of apoptotic cells in response to combined exposure. Collectively, our results suggest the combined effects of heat and pesticide stress cause cellular damage, upregulate oxidative/nitrative stress biomarkers, and increase apoptotic cells, downregulate Na/K-ATPase expression in gills. This provides new evidence for oxidant/antioxidant-dependent mechanisms for downregulation of Na/K-ATPase expression in gills during combined exposure.
Topics: Adenosine Triphosphatases; Animals; Antioxidants; Apoptosis; Gills; Goldfish; Hot Temperature; Oxidative Stress; Pesticides; Sodium-Potassium-Exchanging ATPase; Superoxide Dismutase; Water Pollutants, Chemical
PubMed: 35352221
DOI: 10.1007/s11356-022-19779-7 -
Journal of Water and Health Jun 2024Despite the negative effects that the use of pesticides (such as herbicides and insecticides) have on human health and water resources, a significant portion of the...
Despite the negative effects that the use of pesticides (such as herbicides and insecticides) have on human health and water resources, a significant portion of the world's agricultural production depends on them. The purpose of this study was to determine selected residual concentrations of pesticides (diazinon, ethion, malathion, alachlor, methyl-parathion, trifluralin, atrazine, chlorpyrifos, and azinphos-methyl) in samples from Shiraz potable water sources. For this purpose, water treatment plant, groundwater wells, treated surface water, and a mixture of groundwater and treated surface water were taken. In addition, statistical and risk analyses (carcinogenic and non-carcinogenic) were used. According to the results, chlorpyrifos with 84.4% had the highest removal efficiency and methyl-parathion with 10% had the lowest removal rate in the Shiraz water treatment plant process. The highest mean concentration was related to azinphos-methyl (1.5 μg/L) and chlorpyrifos (0.59 μg/L) in the groundwater samples. All measured compounds in water source samples were below standard levels, except for chlorpyrifos and azinphos-methyl, which were reported in groundwater above the limit recommended by the Environmental Protection Agency (EPA). The results showed that while the selected pesticides measured had a low non-carcinogenic risk for both adults and children, malathion and trifluralin posed a high carcinogenic risk for adults.
Topics: Water Pollutants, Chemical; Herbicides; Risk Assessment; Insecticides; Groundwater; Water Wells; Environmental Monitoring; Water Purification; Drinking Water; Humans; Iran
PubMed: 38935459
DOI: 10.2166/wh.2024.076 -
Spectrochimica Acta. Part A, Molecular... Dec 2019
Corrigendum to "ThThnated Development of a pH assisted AgNP-based Colorimetric Sensor Array for Simultaneous Identification of Phosalone and Azinphosmethyl Pesticides" [Spectrochim. Acta A Mol. Biomol. Spectrosc. 219 (2019) 496-503].
PubMed: 31160184
DOI: 10.1016/j.saa.2019.117155 -
Journal of Biomolecular Structure &... 2022In the present study, combining spectroscopic and molecular modeling techniques has been used to analyze azinphos-methyl binding properties, as an organophosphorus...
In the present study, combining spectroscopic and molecular modeling techniques has been used to analyze azinphos-methyl binding properties, as an organophosphorus pesticide, to bovine serum albumin. The quenching interaction of azinphos-methyl with bovine serum albumin was investigated in an appropriate physiological state (pH = 7.4). Fluorescence spectroscopy, UV-visible spectroscopy, circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR). Findings showed differences in the secondary protein structure microenvironment following interaction with azinphos-methyl. The results from spectroscopic experiments suggest that azinphos-methyl binds to bovine serum albumin residues with a binding constant in the range of 0.099 10-0.209 10 in one binding site (Tyr 160). The experimental results are supported by computational techniques such as docking using a bovine serum albumin crystal model. The results show that azinphos-methyl is linked to the site I of bovine serum albumin (in subdomain IB), and the result was in accordance with the experimental result. Based on the negative ΔG°, ΔH° and ΔS° values, the binding between azinphos-methyl and bovine serum albumin was spontaneous, and docking studies confirmed hydrogen bonding and van der Waals forces between them.Communicated by Ramaswamy H. Sarma.
Topics: Serum Albumin, Bovine; Molecular Docking Simulation; Azinphosmethyl; Organophosphorus Compounds; Pesticides; Binding Sites; Spectrometry, Fluorescence; Circular Dichroism; Spectroscopy, Fourier Transform Infrared; Protein Binding; Thermodynamics
PubMed: 34427168
DOI: 10.1080/07391102.2021.1968954 -
Genes Feb 2023Limb-Girdle Muscular Dystrophy Type R1 (LGMDR1; formerly LGMD2A), characterized by progressive hip and shoulder muscle weakness, is caused by mutations in . In...
Limb-Girdle Muscular Dystrophy Type R1 (LGMDR1; formerly LGMD2A), characterized by progressive hip and shoulder muscle weakness, is caused by mutations in . In zebrafish, mediates Def-dependent degradation of p53 in the liver and intestines. We show that is expressed in the muscle. To model LGMDR1 in zebrafish, we generated three deletion mutants in and a positive-control mutant (Duchenne muscular dystrophy). Two partial deletion mutants showed transcript-level reduction, whereas the RNA-less mutant lacked mRNA. All homozygous mutants were developmentally-normal adult-viable animals. Mutants in were homozygous-lethal. Bathing wild-type and mutants in 0.8% methylcellulose (MC) for 3 days beginning 2 days post-fertilization resulted in significantly pronounced (20-30%) birefringence-detectable muscle abnormalities in mutant embryos. Evans Blue staining for sarcolemma integrity loss was strongly positive in homozygotes, negative in wild-type embryos, and negative in MC-treated mutants, suggesting membrane instability is not a primary muscle pathology determinant. Increased birefringence-detected muscle abnormalities in mutants compared to wild-type animals were observed following induced hypertonia by exposure to cholinesterase inhibitor, azinphos-methyl, reinforcing the MC results. These mutant fish represent a novel tractable model for studying the mechanisms underlying muscle repair and remodeling, and as a preclinical tool for whole-animal therapeutics and behavioral screening in LGMDR1.
Topics: Animals; Zebrafish; Muscular Dystrophies, Limb-Girdle; Muscle, Skeletal; Muscular Dystrophy, Duchenne
PubMed: 36833417
DOI: 10.3390/genes14020492