-
NanoImpact Jan 2022During emission, TiO nanoparticles (NPs) might meet various chemicals, including metal ions and organic compounds in aquatic environments (e.g., surface water,...
During emission, TiO nanoparticles (NPs) might meet various chemicals, including metal ions and organic compounds in aquatic environments (e.g., surface water, sediments). At environmentally safe concentrations, combinations of both TiO NPs and those chemicals might cause cocktail effects (i.e., mixture toxicity) to aquatic organisms. Previous models such as concentration addition and independent action require dose-response curves of single components in the mixtures to predict the mixture toxicity. Structure-activity relationship (QSAR) models might predict the toxicity of nano-mixtures without dose-response curves of single components in the mixtures. However, current quantitative structure-activity relationship (QSAR) models are mainly focused on predicting cytotoxicity (i.e., cell viability) of heterogeneous metallic TiO nanoparticles (NPs) or mixtures of TiO NPs and four metal ions (Cu, Cd, Ni and Zn). To minimize the experimental cost of nano-mixture risk assessment, in this study, we developed novel nano-mixture QSAR models to predict i) EC of 76 nano-mixtures containing TiO NPs and one of eight inorganic/organic compounds (i.e., AgNO, Cd(NO), Cu(NO), CuSO, NaHAsO, NaAsO, Benzylparaben and Benzophenone-3), to Daphnia magna(D. magna), and ii) immobilization of D. magna exposed to one of 98 mixtures containing TiO NPs and one of eleven inorganic/organic compounds (i.e., AgNO, Cd(NO), Cu(NO), CuSO, NaHAsO, NaAsO, Benzylparaben Benzophenone-3, Pirimicarb, Pentabromodiphenyl Ether and Triton X-100). The nano-mixture QSAR models were developed with mixture descriptors (D) combing quantum descriptors of mixture components (e.g., TiO NPs and its partners) by using different machine learning techniques (i.e., random forest, neural network, support vector machine, and multiple linear regression). Nano-mixture QSAR models built with the random forest algorithm and proposed mixture descriptors exhibited good performance for predicting logEC (Adj.R = 0.955 ± 0.003, RMSE = 0.016 ± 0.002, and MAE = 0.008 ± 0.001) and immobilization (Adj.R = 0.888 ± 0.011, RMSE = 11.327 ± 0.730, and MAE = 5.933 ± 0.442). The models developed in this study were implemented in a user-friendly application for assessing the aquatic toxicity of TiO based nano-mixtures.
Topics: Animals; Cadmium; Daphnia; Organic Chemicals; Quantitative Structure-Activity Relationship; Titanium; Water Pollutants, Chemical
PubMed: 35559889
DOI: 10.1016/j.impact.2022.100383 -
Chemosphere Mar 2023Due to their extensive use and high biological activity, insecticides largely contribute to loss of biodiversity and environmental pollution. The regulation of...
Due to their extensive use and high biological activity, insecticides largely contribute to loss of biodiversity and environmental pollution. The regulation of insecticides by authorities is mainly focused on lethal concentrations. However, sub-lethal effects such as alterations in behavior and neurodevelopment can significantly affect the fitness of individual fish and their population dynamics and therefore deserve consideration. Moreover, it is important to understand the impact of exposure timing during development, about which there is currently a lack of relevant knowledge. Here, we investigated whether there are periods during neurodevelopment of fish, which are particularly vulnerable to insecticide exposure. Therefore, we exposed zebrafish embryos to six different insecticides with cholinergic mode of action for 24 h during different periods of neurodevelopment and measured locomotor output using an age-matched behavior assay. We used the organophosphates diazinon and dimethoate, the carbamates pirimicarb and methomyl as well as the neonicotinoids thiacloprid and imidacloprid because they are abundant in the environment and cholinergic signaling plays a major role during key processes of neurodevelopment. We found that early embryonic motor behaviors, as measured by spontaneous tail coiling, increased upon exposure to most insecticides, while later movements, measured through touch-evoked response and a light-dark transition assay, rather decreased for the same insecticides and exposure duration. Moreover, the observed effects were more pronounced when exposure windows were temporally closer to the performing of the respective behavioral assay. However, the measured behavioral effects recovered after a short period, indicating that none of the exposure windows chosen here are particularly critical, but rather that insecticides acutely interfere with neuronal function at all stages as long as they are present. Overall, our results contribute to a better understanding of risks posed by cholinergic insecticides to fish and provide an important basis for the development of safe regulations to improve environmental health.
Topics: Animals; Insecticides; Zebrafish; Diazinon; Cholinergic Agents; Phenotype
PubMed: 36646183
DOI: 10.1016/j.chemosphere.2023.137874 -
Journal of Chromatography. A Oct 2021The low-cost set-up is based on the flexible microfluidic breadboard approach. To avoid the use of electrically driven devices at the high voltage injection end of the...
The low-cost set-up is based on the flexible microfluidic breadboard approach. To avoid the use of electrically driven devices at the high voltage injection end of the capillary pneumatically actuated pumps and valves are employed. It is coupled to the mass spectrometer with a sheathless electrospray obtained in an electrodeless interface configuration. This simplification is achieved by carrying out the analysis in two distinct steps, firstly the separation without the formation of an electrospray, and secondly detection in which the electrospray is created while pumping out the content of the capillary. The performance of the instrument was tested by analysing three benzalkonium ions and the four pesticides pyrifenox, pirimicarb, cyprodinil and pyrimethanil. Detection limits between 0.36 and 0.76 µM and peak reproducibilities between 5.2% and 6.6% (50 µM standards) were obtained for the latter.
Topics: Electrophoresis, Capillary; Pesticides; Reference Standards; Spectrometry, Mass, Electrospray Ionization
PubMed: 34537661
DOI: 10.1016/j.chroma.2021.462533 -
International Journal of Molecular... Mar 2022Glutathione transferases (GSTs; EC 2.5.1.18) form a group of multifunctional enzymes that are involved in phase II of the cellular detoxification mechanism and are...
Glutathione transferases (GSTs; EC 2.5.1.18) form a group of multifunctional enzymes that are involved in phase II of the cellular detoxification mechanism and are associated with increased susceptibility to cancer development and resistance to anticancer drugs. The present study aims to evaluate the ligandability of the human GSTM1-1 isoenzyme (hGSTM1-1) using a broad range of structurally diverse pesticides as probes. The results revealed that hGSTM1-1, compared to other classes of GSTs, displays limited ligandability and ligand-binding promiscuity, as revealed by kinetic inhibition studies. Among all tested pesticides, the carbamate insecticide pirimicarb was identified as the strongest inhibitor towards hGSTM1-1. Kinetic inhibition analysis showed that pirimicarb behaved as a mixed-type inhibitor toward glutathione (GSH) and 1-chloro-2,4-dinitrobenzene (CDNB). To shine a light on the restricted hGSTM1-1 ligand-binding promiscuity, the ligand-free crystal structure of hGSTM1-1 was determined by X-ray crystallography at 1.59 Å-resolution. Comparative analysis of ligand-free structure with the available ligand-bound structures allowed for the study of the enzyme's plasticity and the induced-fit mechanism operated by hGSTM1-1. The results revealed important structural features of the H-site that contribute to xenobiotic-ligand binding and specificity. It was concluded that hGSTM1-1 interacts preferentially with one-ring aromatic compounds that bind at a discrete site which partially overlaps with the xenobiotic substrate binding site (H-site). The results of the study form a basis for the rational design of new drugs targeting hGSTM1-1.
Topics: Binding Sites; Crystallography, X-Ray; Glutathione; Glutathione Transferase; Humans; Kinetics; Ligands; Pesticides; Xenobiotics
PubMed: 35408962
DOI: 10.3390/ijms23073606 -
Nanomaterials (Basel, Switzerland) Aug 2022A three-steps sol-gel method was used to obtain a CuO/SnO/WO heterostructure powder, deposited as film by spray pyrolysis. The porous morphology of the final...
A three-steps sol-gel method was used to obtain a CuO/SnO/WO heterostructure powder, deposited as film by spray pyrolysis. The porous morphology of the final heterostructure was constructed starting with fiber-like WO acting as substrate for SnO development. The SnO/WO sample provide nucleation and grew sites for CuO formation. Diffraction evaluation indicated that all samples contained crystalline structures with crystallite size varying from 42.4 Å (CuO) to 81.8 Å (WO). Elemental analysis confirmed that the samples were homogeneous in composition and had an oxygen excess due to the annealing treatments. Photocatalytic properties were tested in the presence of three pesticides-pirimicarb, S-metolachlor (S-MCh), and metalaxyl (MET)-chosen based on their resilience and toxicity. The photocatalytic activity of the CuO/SnO/WO heterostructure was compared with WO, SnO, CuO, CuO/SnO, CuO/WO, and SnO/WO samples. The results indicated that the three-component heterostructure had the highest photocatalytic efficiency toward all pesticides. The highest photocatalytic efficiency was obtained toward S-MCh (86%) using a CuO/SnO/WO sample and the lowest correspond to MET (8.2%) removal using a CuO monocomponent sample. TOC analysis indicated that not all the removal efficiency could be attributed to mineralization, and by-product formation is possible. CuO/SnO/WO is able to induce 81.3% mineralization of S-MCh, while CuO exhibited 5.7% mineralization of S-MCh. The three-run cyclic tests showed that CuO/SnO/WO, WO, and SnO/WO exhibited good photocatalytic stability without requiring additional procedures. The photocatalytic mechanism corresponds to a Z-scheme charge transfer based on a three-component structure, where CuO exhibits reduction potential responsible for O production and WO has oxidation potential responsible for HO· generation.
PubMed: 35957078
DOI: 10.3390/nano12152648 -
Foods (Basel, Switzerland) Aug 2023In this study, a new approach to pesticide permeation through the apple peel into the pulp is discussed. The tested compounds can be classified, based on mode of action,...
In this study, a new approach to pesticide permeation through the apple peel into the pulp is discussed. The tested compounds can be classified, based on mode of action, as systemic (boscalid, cyprodinil, pirimicarb, propiconazole and tebuconazole) or contact (captan, cypermethrin and fludioxonil) pesticides. The barrier effect was assessed using a Franz flow-type vertical diffusion cell system. A residue analysis was performed using a modified quick, easy, cheap, efficient, rugged and safe (QuEChERS) extraction method coupled to gas chromatography with tandem mass spectrometry (GC-MS/MS). The limits of detection (LODs) ranged between 2.6 µg kg (pirimicarb) and 17 µg kg (captan), with the coefficient of variability (CV) lower than 6%, while recoveries ranged from 85% (boscalid) to 112% (captan) at 0.1 and 1 mg kg spiked levels. The highest peel penetration was observed for pirimicarb, captan and cyprodinil, with cumulative permeations of 90, 19 and 17 µg cm, respectively. The total absorption was in the range from 0.32% (tebuconazole) to 32% (pirimicarb). Only cypermethrin was not quantitatively detected in the pulp, and its use can be recommended in crop protection techniques. The obtained results indicate that molecular weight, octanol-water partition coefficient and water solubility are important parameters determining the process of pesticide absorption.
PubMed: 37685153
DOI: 10.3390/foods12173220 -
Insects Sep 2023The invasive apricot aphid ( Matsumura) is an important pest of apricot trees ( L.). In the presented study, laboratory bioassays using treated leaf disks of apricot...
The invasive apricot aphid ( Matsumura) is an important pest of apricot trees ( L.). In the presented study, laboratory bioassays using treated leaf disks of apricot were conducted to test the efficacy of twelve insecticides according to the maximum field dose. Additionally, dose-response curves were established for selected insecticides, and the effects on colony development were evaluated. Furthermore, a field trial was conducted to investigate the effectiveness of commonly used insecticides in apricot cultivation. The dose-response curves showed LC values ranging from 0.08 mg/L for flupyradifurone, 0.15 mg/L for acetamiprid, 0.70 mg/L for etofenprox, 1.89 mg/L for sulfoxaflor, 2.64 mg/L for pirimicarb, 3.97 mg/L for deltamethrin, up to 6.79 mg/L for tau-fluvalinate. These aforementioned insecticides resulted in mortality rates ranging from 95 to 100% at the field dose. Azadirachtin, flonicamid, and pyrethrins showed mortality rates of 27 to 45%. Spirotetramat reduced the colony development and decreased the number of infested shoots by 86%. Spinosad, which is not recommended against aphids, showed minimal impact; reducing the number of exuviae in nymphs in the colony development bioassay. It can be concluded that the majority of the tested insecticides are effective against .
PubMed: 37754715
DOI: 10.3390/insects14090746 -
Asian Pacific Journal of Tropical... Jan 2017To investigate protective effects of Spilanthes acmella (S. acmella) Murr. extracts against pesticide-induced neuronal cells death and to elucidate the underlying...
OBJECTIVE
To investigate protective effects of Spilanthes acmella (S. acmella) Murr. extracts against pesticide-induced neuronal cells death and to elucidate the underlying molecular mechanism in dopaminergic (SH-SY5Y) cells lines.
METHODS
Cell viability of SH-SY5Y cells was studied by treating the cells with various concentration of pirimicarb for 24 h. Neuroprotective effect of S. acmella Murr. extracts was investigated by adding the plant extracts to the medium for 24 h prior to the incubation with 100 μM HO or with pirimicarb for 24 h. Control-untreated cells were incubated with the culture medium. Cell viability was measured by MTT assay, calpain and calpastatin expressions were analyzed by Western blotting and immunocytochemistry.
RESULTS
Pretreatment of SH-SY5Y cells with S. acmella Murr. extracts (1 μg/mL) for 24 h significantly increased the dopaminergic neurons in pirimicarb-induced neurotoxicity. In addition, pretreatment with the S. acmella Murr. extracts led to decreased calpain but increased calpastatin protein levels.
CONCLUSION
S. acmella Murr. extracts exerted neuroprotective effect, via an alteration of calcium homeostasis, against pirimicarb induced neurotoxicity. The S. acmella Murr. might be a potential natural candidate with neuroprotective activity.
PubMed: 28107862
DOI: 10.1016/j.apjtm.2016.11.012 -
Scientific Reports Jan 2018Pesticide exposure during fetal life can lead to low birth weight and is commonly observed in reproductive toxicology studies. Associations have also been found in low...
Pesticide exposure during fetal life can lead to low birth weight and is commonly observed in reproductive toxicology studies. Associations have also been found in low birth weight babies born from pesticide-exposed gardeners. Since low birth weight is also linked to metabolic disorders, it can be speculated that early life exposure to pesticides could increase the risk of becoming obese or developing diabetes later in life. We have analyzed potential long-term effects of gestational and lactational exposure to a low dose mixture of six pesticides that individually can cause low birth weight: Cyromazine, MCPB, Pirimicarb, Quinoclamine, Thiram, and Ziram. Exposed male offspring, who were smaller than controls, displayed some degree of catch-up growth. Insulin and glucagon regulation was not significantly affected, and analyses of liver and pancreas did not reveal obvious histopathological effects. Efforts towards identifying potential biomarkers of metabolic disease-risk did not result in any strong candidates, albeit leptin levels were altered in exposed animals. In fat tissues, the key genes Lep, Nmb and Nmbr were altered in high dosed offspring, and were differentially expressed between sexes. Our results suggest that early-life exposure to pesticides may contribute to the development of metabolic disorders later in life.
Topics: 2-Methyl-4-chlorophenoxyacetic Acid; Adipose Tissue; Animals; Butyrates; Carbamates; Diabetes Mellitus; Female; Fetal Growth Retardation; Infant, Low Birth Weight; Naphthoquinones; Pesticides; Pregnancy; Prenatal Exposure Delayed Effects; Pyrimidines; Rats; Rats, Wistar; Thiram; Triazines; Ziram
PubMed: 29321614
DOI: 10.1038/s41598-017-18626-x -
Archives of Toxicology Dec 2020In chemical risk assessment, default uncertainty factors are used to account for interspecies and interindividual differences, and differences in toxicokinetics and... (Comparative Study)
Comparative Study
Acetylcholinesterase inhibition in electric eel and human donor blood: an in vitro approach to investigate interspecies differences and human variability in toxicodynamics.
In chemical risk assessment, default uncertainty factors are used to account for interspecies and interindividual differences, and differences in toxicokinetics and toxicodynamics herein. However, these default factors come with little scientific support. Therefore, our aim was to develop an in vitro method, using acetylcholinesterase (AChE) inhibition as a proof of principle, to assess both interspecies and interindividual differences in toxicodynamics. Electric eel enzyme and human blood of 20 different donors (12 men/8 women) were exposed to eight different compounds (chlorpyrifos, chlorpyrifos-oxon, phosmet, phosmet-oxon, diazinon, diazinon-oxon, pirimicarb, rivastigmine) and inhibition of AChE was measured using the Ellman method. The organophosphate parent compounds, chlorpyrifos, phosmet and diazinon, did not show inhibition of AChE. All other compounds showed concentration-dependent inhibition of AChE, with ICs in human blood ranging from 0.2-29 µM and ICs ranging from 0.1-18 µM, indicating that AChE is inhibited at concentrations relevant to the in vivo human situation. The oxon analogues were more potent inhibitors of electric eel AChE compared to human AChE. The opposite was true for carbamates, pointing towards interspecies differences for AChE inhibition. Human interindividual variability was low and ranged from 5-25%, depending on the concentration. This study provides a reliable in vitro method for assessing human variability in AChE toxicodynamics. The data suggest that the default uncertainty factor of ~ 3.16 may overestimate human variability for this toxicity endpoint, implying that specific toxicodynamic-related adjustment factors can support quantitative in vitro to in vivo extrapolations that link kinetic and dynamic data to improve chemical risk assessment.
Topics: Acetylcholinesterase; Animals; Bayes Theorem; Biological Variation, Population; Cholinesterase Inhibitors; Dose-Response Relationship, Drug; Electrophorus; Female; GPI-Linked Proteins; Humans; Male; Proof of Concept Study; Reproducibility of Results; Risk Assessment; Species Specificity; Toxicity Tests; Toxicokinetics; Uncertainty
PubMed: 33037899
DOI: 10.1007/s00204-020-02927-8