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RSC Advances Jun 2022To achieve rapid and convenient on-site pretreatment and determination of parathion-methyl, a density-adjusted liquid-phase microextraction with smartphone digital image...
Density-adjusted liquid-phase microextraction with smartphone digital image colorimetry to determine parathion-methyl in water, fruit juice, vinegar, and fermented liquor.
To achieve rapid and convenient on-site pretreatment and determination of parathion-methyl, a density-adjusted liquid-phase microextraction with smartphone digital image colorimetry was established to detect parathion-methyl in food samples. In this study, the environmentally friendly biomass-derived solvent guaiacol was used as the extractant. Salt and water, as density regulators, realized the two movements (floating-sinking) of the extractant and full contact between the extractant and the sample solution to establish an environmentally friendly, fast, and efficient pretreatment method. Under strong alkaline conditions, parathion-methyl generated a yellow product; then, a smartphone was used to obtain the image of the yellow product for intensity analysis. Parathion-methyl has a good linear relationship in the range of 0.01-1 mg L, and the limits of detection and quantification are 0.003 and 0.01 mg L, respectively. This method has been successfully applied to the determination of parathion-methyl in spiked water, fruit juice, vinegar, and fermented liquor with a recovery of 91.6-106.5% and a relative standard deviation of 0.6-6.0%. The established density-adjusted liquid phase microextraction with smartphone digital image colorimetry is rapid, convenient, and environmentally friendly for the determination of parathion-methyl in food samples.
PubMed: 35800312
DOI: 10.1039/d2ra02760g -
Chemico-biological Interactions Aug 2022Epidemiological evidence suggests that people chronically exposed to organophosphorus pesticides are at increased risk of neurodegenerative disease. Covalently linked...
Epidemiological evidence suggests that people chronically exposed to organophosphorus pesticides are at increased risk of neurodegenerative disease. Covalently linked amyloid beta dimers have been isolated from the brains of Alzheimer's patients. The toxic forms of amyloid beta are amyloid dimers that spontaneously oligomerize. In the present report we treated recombinant and synthetic amyloid beta (1-42) with 1 mM chlorpyrifos oxon or 1 mM paraoxon. The trypsin-digested samples were analyzed by liquid chromatography tandem mass spectrometry on an Orbitrap Fusion Lumos mass spectrometer. Data were searched with Protein Prospector software. We found two new types of crosslinks in amyloid dimers. An isopeptide Asp-Asp link occurred between the N-terminal amine of Asp 1 in one peptide and the beta carboxyl group of Asp 1 in another peptide. An Asp-Arg link occurred between the guanidino group of Arg 5 in one peptide and the beta carboxyl group of Asp 1 in another peptide. These results show that the active metabolites of the pesticides chlorpyrifos and parathion catalyze the crosslinking of amyloid beta (1-42) into toxic dimers. It was concluded that the increased risk of neurodegenerative disease in people exposed to organophosphorus pesticides could be explained by the crosslinking activity of these chemicals. Data are available via ProteomeXchange with identifier PXD034163.
Topics: Alzheimer Disease; Amyloid beta-Peptides; Chlorpyrifos; Humans; Neurodegenerative Diseases; Organophosphorus Compounds; Peptide Fragments; Pesticides
PubMed: 35779611
DOI: 10.1016/j.cbi.2022.110029 -
Microbiological Research Aug 2022Microbes are crucial in removing various xenobiotics, including pesticides, from the environment, specifically by mineralizing these hazardous pollutants. However, the...
Microbes are crucial in removing various xenobiotics, including pesticides, from the environment, specifically by mineralizing these hazardous pollutants. However, the specific procedure of microbe-mediated pesticide degradation and its consequence on the environment remain elusive owing to limitations in culturing techniques. Therefore, in this study, we have investigated i) the physicochemical and elemental compositions of PCAS (pesticide-contaminated agricultural soils) and NS (natural soils); ii) the bacterial communities and degradation pathways, as well as some novel biodegradation genes (BDGs) and pesticide degradation genes (PDGs) across two different landscapes (PCAS and NS) by applying high-throughput sequencing. The chemical and elemental composition analyses showed that all nutrients (P, K, N, S, Mn, B, and Zn) were significantly higher in PCAS than in NS (p ≤ 0.05). The results of the 16S rRNA amplicon sequencing analysis of pesticide-contaminated (PCAS-1, PCAS-2, PCAS-3, PCAS-4) samples showed that the relative abundance of the phylum Proteobacteria (30-36%) > Actinobacteria (15-20%) > Firmicutes (13-14%) > Bacteroidetes (7-13%), were higher compared to the natural soil (NS-1, NS2). Consistent with this, a phylogenetic shift was observed with (alpha, beta, and gamma Proteobacteria) being abundant in PCAS, whereas delta and epsilon groups were more prevalent in NS. The functional characterization of the PCAS and NS by PICRUSt2 revealed that bacterial communities play a significant role in pesticide metabolism. Predictive metagenome analysis of contaminated soils showed the role of core degrading genes in membrane transport, stress response, regulatory genes, resource transport, and environmental sensing. Furthermore, 14 BDGs and 30 PDGs were examined, with a relative abundance of 0.081-1.029 % and 0.107-0.8903 % in each PCAS, respectively. The major BDGs and PDGs, with the compounds they hydrolyze, include ppo (polyphenol oxidase and laccase), CYP (cytochrome p450 protein), lip gene (lignin peroxidase), similarly, among the PDGs mhel (carbendazim), opd (organophosphate), mpd (methyl parathion), atzA, atzB, atzD, atzF and trzN (atrazine), chd (chlorothalonil), hdx (metamitron), hdl-1 (isoproturon) and fmo (nicosulfuron). Overall, our findings demonstrated the significance of utilizing metagenomic methods to predict microbial aided degradation in the ecology of contaminated environments.
Topics: Bacteria; Biodegradation, Environmental; Metagenome; Pesticides; Phylogeny; RNA, Ribosomal, 16S; Soil; Soil Microbiology; Soil Pollutants
PubMed: 35660194
DOI: 10.1016/j.micres.2022.127081 -
Se Pu = Chinese Journal of... Jun 2022A rapid screening method for 84 pesticide residues in dendrobium perfringens parent material with different polarities was developed using a Sin-QuEChERS Nano clean-up...
A rapid screening method for 84 pesticide residues in dendrobium perfringens parent material with different polarities was developed using a Sin-QuEChERS Nano clean-up column combined with gas chromatography-tandem mass spectrometry (GC-MS/MS). The differences in extraction efficiency of the targets were compared with different extraction solvents (acetonitrile containing 1% acetic acid, acetone) and methods (immersion with or without water). The purification effect and extraction recoveries of Sin-QuEChERS Nano method and classical dispersive solid-phase extraction (dSPE), solid-phase extraction (SPE) and QuEChERS were systematically compared using samples. The differences in matrix effects between the Sin-QuEChERS Nano method, which was more effective in purification, and the dSPE method were also analyzed. The purification effects of three commercially available Sin-QuEChERS Nano purification columns (simple matrix purification column, complex matrix purification column and herbal purification column) were compared. The applicability of the purification methods were also verified by using different parts of samples (stems, leaves and flowers). From the results, it could be concluded that weighing 2.00 g and the samples in 5 mL of water for 20 min, followed by extraction with acetonitrile containing 1% acetic acid was more effective. The average extraction recovery of the target components by Sin-QuEChERS Nano purification method was 90.5%, which further identified Sin-QuEChERS Nano-Chinese medicine purification column as the preferred purification column for dendrobium purification. The target components were separated by a DB-1701MS quartz capillary column (30 m×0.25 mm×0.25 μm) with programmed temperature rise, detected by multiple reaction monitoring (MRM) mode, and quantified by matrix-matched solution external standard method. The GC-MS/MS assay was used for the methodological validation of the 84 representative pesticides within and was carried out by GC-MS/MS detection method. The results indicated that the targets showed excellent linear correlation in different scopes with correlation coefficients () >0. 990. The limits of detection (LODs, =3) of the method were 1.5 to 5.8 μg/kg, and the limits of quantification (LOQs, =10) ranged from 5.0 to 15.0 μg/kg. The spiked recoveries of the target pesticides under different spiked levels were 68.7%-116.2%, and the relative standard deviations (RSDs, =6) were less than 15%. Compared to other typical pretreatment methods, the Sin-QuEChERS Nano method provided better performance in terms of purification. The method not only effectively removed pigments, organic acids, and alkaline interferents, but also saved preparation time. Losses due to solvent transfer were also avoided and no further vortexing or centrifugation was required, making it a simplified and effective extraction and purification procedure. The method was sensitive, rapid, simple and reliable. It effectively improved the detection efficiency during the rapid screening of pesticides in dendrobium and presented a strong practical application value. In addition, the developed method could further expand the types of target pesticides and could be used to detect more pesticide residues in foods and Chinese herbal medicine. The established Sin-QuEChERS Nano method was used for the analysis of authentic samples. The applicability of the method was evaluated by analyzing a total of 80 samples collected from Anlong, Libo, Dushan, and Yanhe County in Guizhou Province. The types of samples included dendrobium maple, (flowers, stems, leaves) and (flowers, stems, leaves, powder, tablets). At least one pesticide residue was detected in 12 samples, with a detection rate of 15%. The five pesticides with higher detection rates and residues were chlorpyrifos (0.08-0.5 mg/kg), chlorothalonil (0.06-3.2 mg/kg), propanil zinc (0.03-0.15 mg/kg), methyl parathion (0.04-0.23 mg/kg) and cyhalothrin (0.10-2.68 mg/kg). Except for the pesticides in maximum residue limits (MRLs), the pesticide residues detected from dendrobium samples were below the limits set by Chinese national standard (GB 2763-2021) and local standard DBS 52/048-2020.
Topics: Acetonitriles; Dendrobium; Gas Chromatography-Mass Spectrometry; Pesticide Residues; Pesticides; Solid Phase Extraction; Solvents; Tandem Mass Spectrometry; Water
PubMed: 35616202
DOI: 10.3724/SP.J.1123.2021.12010 -
Analytical and Bioanalytical Chemistry Jun 2022Pesticides such as organothiophosphates (OTPs) are neurotoxically active and enter the aquatic environment. Bioassays, using acetylcholinesterase (AChE), a suitable...
High-performance thin-layer chromatography in combination with an acetylcholinesterase-inhibition bioassay with pre-oxidation of organothiophosphates to determine neurotoxic effects in storm, waste, and surface water.
Pesticides such as organothiophosphates (OTPs) are neurotoxically active and enter the aquatic environment. Bioassays, using acetylcholinesterase (AChE), a suitable substrate and reactant, can be applied for the photometric detection of AChE-inhibiton (AChE-I) effects. The oxidized forms of OTPs, so-called oxons, have higher inhibition potentials for AChE. Therefore, a higher sensitivity is achieved for application of oxidized samples to the AChE assay. In this study, the oxidation of malathion, parathion, and chlorpyrifos by n-bromosuccinimide (NBS) was investigated in an approach combining high-performance thin-layer chromatography (HPTLC) with an AChE-I assay. Two AChE application approaches, immersion and spraying, were compared regarding sensitivity, precision, and general feasibility of the OTP effect detection. The oxidation by NBS led to an activation of the OTPs and a strong increase in sensitivity similar to the oxons tested. The sensitivity and precision of the two application techniques were similar, although the spray method was slightly more sensitive to the oxidized OTPs. The 10% inhibition concentrations (IC) for the spray approach were 0.26, 0.75, and 0.35 ng/spot for activated malathion, parathion, and chlorpyrifos, respectively. AChE-I effect recoveries in samples from a stormwater retention basin and receiving stream were between 69 and 92% for malathion, parathion, and chlorpyrifos. The overall workflow, including sample enrichment by solid-phase extraction, HPTLC, oxidation of OTPs, and AChE-I assay, was demonstrated to be suitable for the detection of AChE-I effects in native water samples. An effect of unknown origin was found in a sample from a stormwater retention basin.
Topics: Acetylcholinesterase; Biological Assay; Chlorpyrifos; Cholinesterase Inhibitors; Chromatography, Thin Layer; Insecticides; Malathion; Organothiophosphates; Parathion; Water
PubMed: 35583680
DOI: 10.1007/s00216-022-04068-6 -
RSC Advances Oct 2021Developing a new functional sensitized structure for improving the inherent property of photoactive materials and selecting an efficient electron donor as a...
A one-step hydrothermal route to fabricate a ZnO nanorod/3D graphene aerogel-sensitized structure with enhanced photoelectrochemistry performance and self-powered photoelectrochemical biosensing of parathion-methyl.
Developing a new functional sensitized structure for improving the inherent property of photoactive materials and selecting an efficient electron donor as a photoelectrochemical (PEC) signal amplification strategy are crucial for achieving excellent PEC biosensors. Herein, we present a facile one-pot hydrothermal strategy for fabricating ZnO nanorod-decorated 3D graphene aerogels (ZnO/GAs). In this nanoarchitecture, GAs act as a new generation enhanced carrier, which can effectively improve the photoactivity of ZnO under visible light by enhancing the interfacial charge transfer. In addition, the as-prepared ZnO/GA nanocomposites exhibited two times higher photocurrent intensity than that of ZnO/graphene. Furthermore, we developed a novel self-powered PEC biosensor based on a ZnO/GAs sensitized structure with the amplification of enzymolysis products for the detection of parathion-methyl. Thiocholin, as a sacrificial electron donor, which is produced from the hydrolysis of acetylthiocholine catalyzed by acetylcholinesterase (AChE), can further significantly improve the photocurrent. Then, the inhibition of AChE activity by parathion-methyl prevented the production of thiocholine, resulting in an obvious decrease in photocurrents. Based on the above results, we fabricated an AChE-based self-powered PEC biosensor for the sensitive and selective determination of parathion-methyl with a linear range of 0.1 ng mL to 0.1 μg mL and a detection limit of 0.03 ng mL (S/N = 3). This PEC biosensing strategy not only gives insights into using GAs as a novel sensibilizer to improve the PEC nature of semiconductors but also provides a promising flexible platform for organophosphorus pesticide detection.
PubMed: 35493183
DOI: 10.1039/d1ra06339a -
RSC Advances May 2021Regenerated bead cellulose is a promising material with excellent mechanical and rheological properties, ideally suited for advanced environmental applications. By...
Regenerated bead cellulose is a promising material with excellent mechanical and rheological properties, ideally suited for advanced environmental applications. By introducing the amidoxime functional group into the glucose unit at the C-6 position, highly effective reactive sorbent was prepared and used to destroy priority hazardous substances such as organophosphate pesticides or nerve-paralytic chemical warfare agents (CWAs). Quantum mechanical (QM) calculations were performed to study the interactions of organophosphates with amidoxime functional groups at the molecular level. It was found that the energetic reaction barrier of the rate-limiting step is markedly reduced (from 31.40 to 11.37 kcal mol) in the case of the amidoxime-catalysed degradation of parathion methyl, which resulted in a dramatic increase in the degradation rate; this was fully confirmed by experiments, in which the pesticide degradation proceeded at the time scale of several hours ( = 20-30 hours at pH 7.22).
PubMed: 35480219
DOI: 10.1039/d1ra01125a -
Nanomaterials (Basel, Switzerland) Apr 2022Flexible sensors are highly advantageous for integration in portable and wearable devices. In this work, we propose and validate a simple strategy to achieve whole...
Flexible sensors are highly advantageous for integration in portable and wearable devices. In this work, we propose and validate a simple strategy to achieve whole wafer-size flexible SERS substrate via a one-step metal-assisted chemical etching (MACE). A pre-patterning Si wafer allows for PSi structures to form in tens of microns areas, and thus enables easy detachment of PSi film pieces from bulk Si substrates. The morphology, porosity, and pore size of PS films can be precisely controlled by varying the etchant concentration, which shows obvious effects on film integrity and wettability. The cracks and self-peeling of Psi films can be achieved by the drying conditions after MACE, enabling transfer of Psi films from Si wafer to any substrates, while maintaining their original properties and vertical alignment. After coating with a thin layer of silver (Ag), the rigid and flexible PSi films before and after transfer both show obvious surface-enhanced Raman scattering (SERS) effect. Moreover, flexible PSi films SERS substrates have been demonstrated with high sensitivity (down to 2.6 × 10 g/cm) for detection of methyl parathion (MPT) residues on a curved apple surface. Such a method provides us with quick and high throughput fabrication of nanostructured materials for sensing, catalysis, and electro-optical applications.
PubMed: 35407309
DOI: 10.3390/nano12071191 -
Toxicology Reports 2022Organophosphorus pesticides (OPPs) cause great risk to human health as they are used globally. Therefore, the purpose of this research was to determine the total...
Organophosphorus pesticides (OPPs) cause great risk to human health as they are used globally. Therefore, the purpose of this research was to determine the total phenolics, flavonoids, and antioxidant activity of agricultural waste, as well as to control the pesticide residues (diazinon, and parathion) at a laboratory scale level using dried-milled fruit wastes. The pesticide residues parathion and diazinon were used at concentrations of 0.094, and 1.90 mg/mL respectively. The fruit wastes used in this study were orange and banana peels, as well as date stones, and they were used in two concentrations (3 and 9 g/30 mL deionized water). The total phenolic and flavonoid contents and the antioxidant activity were measured in fruit wastes. Also, the Fourier transmitted infrared (FTIR) spectra of fruit wastes were established to figure out the nature of the functional groups found before and after pesticide residues removal. The ability of fruit wastes to remove pesticides residues was determined using Gas Chromatography/Mass spectrometry (GC/MS). Data showed that date stones contained a higher amount of total phenolic content than orange and banana peels. However, orange peels contained a higher amount of total flavonoid contents than those of date stones and banana peels. As for antioxidant activity, banana peels recorded the higher antioxidant activity, followed by orange peels and date stones respectively. Results revealed that there was no relation between total phenolic content, total flavonoid content, and antioxidant activity. Results also indicated that date stones at a concentration of 9 g successfully reduced diazinon (81.18%), followed by banana (63.86%) and orange peels (43.42%) respectively, whereas parathion was reduced by banana peels at a concentration of 9 g (50.34%), followed by orange peels (45.28%), and date stones (39.52%) respectively. This study demonstrated that agricultural wastes were effective in the adsorption of diazinon from water, and their use is considered safe for the environment.
PubMed: 35399213
DOI: 10.1016/j.toxrep.2022.03.038 -
Data in Brief Apr 2022Cytochrome P450 2B6 (CYP2B6) is a human enzyme important in chemical detoxification, steroid and fatty acid metabolism that is primarily hepatic. Therefore, induction or...
Cytochrome P450 2B6 (CYP2B6) is a human enzyme important in chemical detoxification, steroid and fatty acid metabolism that is primarily hepatic. Therefore, induction or inhibition of CYP2B6 may perturb endo- and xenobiotic metabolism and cause adverse reactions. Recent research indicates that mice lacking Cyp2b enzymes are obese with liver steatosis [1] (Heintz et al., , 70:125-137, 2019). Current work is underway to determine the role of CYP2B6 in obesity and fatty acid metabolism, and CYP2B6 fluorescent inhibition assays were used to determine the IC50s of multiple industrial chemicals, pesticides, bile acids, steroids, and fatty acids. In many cases, inhibition of CYP3A4 was also performed in comparison because CYP3A4 is the most abundant hepatic detoxification CYP and therefore by abundance alone may also play a key role in the chemical's metabolism. Further, using the ratio of comparative potency of these compounds for CYP2B6 and CYP3A4, specificity can be estimated for these CYP2B6 inhibitors. These results indicate strong preferential inhibition (greater than 10-fold) of CYP2B6 and include lithocholic acid, arachidonic acid, atrazine, chlorpyrifos, endosulfan, parathion, and nonylphenol. Estradiol was a strong preferential inhibitor of CYP3A4. Other screened CYP2B6 inhibitors include triclosan, ticlopidine, jet fuel, docosahexaenoic acid, linoleic acid, linolenic acid, oleic acid, lithocholic acid, butylate, hexachlorocyclohexane, vinclozolin, pentachlorophenol, metalachlor, butylate, diazinon, avermectin, tribufos, ticlopidine, and bisphenol A. Documentation of xenobiotic and endobiotic inhibition by these CYPs is necessary for proper modeling of the effects of diet, chemical exposure or even mixtures on drug metabolism and potential adverse reactions.
PubMed: 35282180
DOI: 10.1016/j.dib.2022.108013