Steric and energetic studies on the influence of cellulose on the adsorption effectiveness of Mg trapped hydroxyapatite for enhanced remediation of chlorpyrifos and omethoate pesticides.

Magnesium-trapped hydroxyapatite (Mg.HP) was hybridized with cellulose fiber to produce a bio-composite (CLF/HP) with enhanced adsorption affinities for two types of toxic pesticides (chlorpyrifos (CF) and omethoate (OM)). The enhancement influence of the hybridized cellulose on the adsorption performances of Mg.HP was illustrated based on the determined steric and energetic factors. The computed CF and OM adsorption performances of CLF/HP during the saturation phases are 279.8 mg/g and 317.9 mg/g, respectively, which are significantly higher than the determined values using Mg/HP (143.4 mg/g (CF) and 145.3 mg/g (OM)). The steric analysis demonstrates a strong impact of the hybridization process on the reactivity of the surface of the composite. While CLF/HP reflects effective uptake site densities (Nm) of 93.3 mg/g (CF) and 135.3 mg/g (OM), the estimated values for Mg.HP are 51.2 mg/g (CF) and 46.11 mg/g (OM), which explain the reported enhancement in the adsorption performances of the composite. The capacity of each uptake site to be occupied with more than one molecule (n (CF) = 3-3.74 and n (OM) = 2.35-3.54) suggests multimolecular uptake. The energetic factors suggested physical mechanistic processes of spontaneous and exothermic behaviors either during the uptake of CF or OM.

A photoelectrochemical aptasensor for omethoate determination based on a photocatalysis of CeO2@MnO2 heterojunction for glucose oxidation.

In the present work, we developed a photoelectrochemical aptasensor to determine omethoate (OMT) based on the dual signal amplification of CeO2@MnO2 photocatalysis for glucose oxidation and exonuclease I-assisted cyclic catalytic hydrolysis. CeO2@MnO2 heterojunction material prepared by hydrothermal method was linked with captured DNA (cDNA) and then assembled on the ITO conductive glass to form ITO/CeO2@MnO2-cDNA, which exhibited significant photocurrent response and good photocatalytic performance for glucose oxidation under visible light irradiation, providing the feasibility for sensitive determining OMT. After binding with the aptamer of OMT (apt), the formation of rigid double stranded cDNA/apt kept CeO2@MnO2 away from ITO surface, which ensured a low photocurrent background for the constructed ITO/CeO2@MnO2-cDNA/apt aptasensor. In the presence of target OMT, the restoration of the cDNA hairpin structure and the exonuclease I-assisted cyclic catalytic hydrolysis led to the generation and amplification of measurement photocurrent signals, and allowed the aptasensor to have an ideal quantitative range of 0.01-10.0 nM and low detection limit of 0.0027 nM. Moreover, the aptasensor has been applied for selective determination of OMT in real samples with good precision of the relative standard deviation less than 6.2 % and good accuracy of the recoveries from 93 % to 108 %. What's more, the aptasensor can be used for other target determination only by replacing the captured DNA and corresponding aptamer.

Homogeneous photoelectrochemical biosensor for sensitive detection of omethoate via ALP-mediated pesticide assay and Bi2S3@Bi2Sn2O7 heterojunction as photoactive material.

A simple homogeneous photoelectrochemical (PEC) sensing platform based on an alkaline phosphatase (ALP)-mediated pesticide assay was established for the sensitive detection of omethoate (OM). The Bi2S3@Bi2Sn2O7 heterojunction was used as a photoactive material to provide stable background photocurrent signals. The inhibition of OM on ALP and PEC determination was carried out in the homogeneous system. In the absence of OM, dephosphorylation of L-ascorbic acid 2-phosphate trisodium salt (AAP) was catalyzed by ALP to produce the enzyme-catalyzed product (L-ascorbic acid, AA). AA, as an electron donor, could capture photogenerated holes on the Bi2S3@Bi2Sn2O7 heterojunction, thus inhibiting the recombination of electron holes to achieve an increase of the photocurrent signal. When the OM was introduced, the enzyme activity of ALP was reduced due to the organophosphorus pesticides (OPs)-based enzyme inhibition, and the AA produced by catalytic hydrolysis was also reduced, thus reducing the photocurrent signal. Compared with the traditional PEC sensor for OPs, this homogeneous PEC sensor avoided immobilization procedures, covalent labeling, separation, and the steric hindrance effect caused by immobilized biomolecules, which achieved high recognition efficiency and caused a reduction in analysis time. Additionally, an ALP-mediated pesticide assay for the determination of OPs with a simplified experimental process further improved the stability and reproducibility of the PEC sensor. The PEC sensor showed high sensitivity to the target OM within a dynamic range of 0.05 ~ 500 ng mL-1, and the detection limit was 0.0146 ng mL-1. Additionally, the PEC biosensing system showed good selectivity and anti-interference ability, and exhibited a satisfactory result in spinach and mustard samples. A homogeneous PEC biosensor based on ALP inhibition strategy was constructed for OM detection in vegetable samples via Bi2S3@Bi2Sn2O7 heterojunction as the photoactive substrate material.

Simultaneous determination of dimethoate and its metabolite omethoate in curry leaf using LC-MS/MS and risk assessment.

This study presents the method development, validation, and simultaneous determination of dimethoate and its metabolite omethoate in curry leaf. Samples were extracted following modified quick, easy, cheap, effective, rugged, and safe extraction protocol and analyzed using liquid chromatography-tandem mass spectrometry. The limit of quantification in the matrix was 0.005 µg g-1 for dimethoate and omethoate. Extraction using acetonitrile recorded the average recoveries in the range of 82.25 to 112.97% for dimethoate and 85.57 to 107.22% for omethoate at 0.005, 0.025 and 0.050 µg g-1 fortification levels and relative standard deviation less than 5%. Similarly, the relative standard deviation values for intraday (Repeatability) and interday (Reproducibility) tests were less than 15%. Dissipation kinetics of dimethoate 30% emulsifiable concentrate at 200 and 400 g a.i h-1 recorded initial deposits of 5.20 and 10.05 µg g-1 and 0.33 and 0.48 µg g-1 for dimethoate and omethoate, respectively, and half-life of 3.07 and 3.34 days. The estimated hazard index value found more than one at a day after dimethoate application. It is not safe for consumer health to use curry leaves in the initial days after application.

The association between polymorphisms in miRNA and the cholinesterase activity of workers in an omethoate-exposed environment.

To explore the association between polymorphisms in microRNAs (miRNAs) and the cholinesterase (ChE) activity in omethoate-exposed workers, we recruited 180 omethoate-exposed workers and 115 controls to measure their ChE activity using acetylcholine and dithio-bis-(nitrobenzoic acid) and genotype susceptible SNPs in their miRNA by time-of-flight mass spectrometry. ChE activity in the exposure group was lower than that in the control group (P < 0.001). The analysis of covariance result showed that ChE activity was lower in the (- -/- T) genotype in miR-30a rs111456995 (1.97 ± 0.47) than in the TT genotype (2.23 ± 0.59) of the exposure group (P = 0.004). Multivariate linear regression was performed to find influencing factors on ChE activity, and variables kept in the model included omethoate exposure (b = -1.094, P < 0.001), gender (b = -0.381, P < 0.001), miR-30a rs111456995 (- -/- T)(b = -0.248, P < 0.001), and drinking (b = 0.258, P =0.019). The results suggest that individuals carrying a (- -/- T) genotype in miR-30a rs111456995 were more susceptible to damage in their cholinesterase induced by omethoate exposure.

Sulphur-doped graphene quantum dot based fluorescent turn-on aptasensor for selective and ultrasensitive detection of omethoate.

Development of selective, ultra-sensitive, rapid and facile methods for the detection of chemical residues of toxic pesticides and hazardous chemicals are quite important in food safety, environmental monitoring and safeguarding public health. Herein, we presented a fluorescent turn-on aptasensor based on sulphur-doped graphene quantum dot (S-GQD) utilizing specific recognition and binding property of aptamer for the ultra-sensitive and selective detection of omethoate (OM) which is a systemic organophosphorus pesticide. The detection method is based on tuning aggregation-disaggregation mechanism of S-GQD by way of conformational alteration of the recognition probe. Fluorescence 'turn-on' process includes aggregation-induced quenching of S-GQD with aptamer via S-GQD-aptamer complex formation and its subsequent fluorescence recovery with the addition of OM by structural switching of S-GQD-aptamer complex to aptamer-omethoate complex. The reported 'switch-on' aptasensor has exhibited a low limit of detection of 0.001 ppm with high selectivity for OM over other pesticides.

Nanoparticles-doped induced defective ZIF-8 as the novel cathodic luminophore for fabricating high-performance electrochemiluminescence aptasensor for detection of omethoate.

Although the use of omethoate (OMT) for pests control is enormously economically beneficial for agricultural production, the high toxicity of OMT to nontarget organisms has resulted in the contamination of soil, river water, and food materials. Developing sensitive and convenient techniques to detect OMT residues is vital to society. Electrochemiluminescence (ECL) is a powerful analytical tool and has been widely applied in biosensors. To boost the co-reaction efficiency and ECL intensity, we introduced defective ZIF-8 as the novel cathodic luminophore. At the same time, defect generated by the doping of MoTe2 nanoparticles into ZIF-8 could easily electrocatalytic reduce the co-reactor S2O82- to SO4•-. Hence, based on the catalysis of defective ZIF-8, the ECL intensity of MoTe2/ZIF-8 nanocomposites is much higher than both ZIF-8 and MoTe2 nanoparticles. By integration of as-prepared materials with specificity omethoate aptamer, the ECL sensor showed a broad linear range (10-10 g L-1 and 10-5 g L-1) and a comparatively low detection limit (3.3 × 10-11 g L-1). Besides, the ECL aptasensor appeared a good practical performance to detect potato and spinach extraction samples, which proposed a promising guideline for developing ECL aptasensors with high efficiency.

Impaired neuromuscular function by conjoint actions of organophosphorus insecticide metabolites omethoate and cyclohexanol with implications for treatment of respiratory failure.

BACKGROUND: Ingestion of agricultural organophosphorus insecticides is a significant cause of death in rural Asia. Patients often show acute respiratory failure and/or delayed, unexplained signs of neuromuscular paralysis, sometimes diagnosed as "Intermediate Syndrome". We tested the hypothesis that omethoate and cyclohexanol, circulating metabolites of one agricultural formulation, cause muscle weakness and paralysis. METHODS: Acetylcholinesterase activity of insecticide components and metabolites was measured using purified enzyme from eel electroplaque or muscle homogenates. Mechanomyographic recording of pelvic limb responses to nerve stimulation was made in anaesthetized pigs and isometric force was recorded from isolated nerve-muscle preparations from mice. Omethoate and cyclohexanol were administered intravenously or added to physiological saline bathing isolated muscle. We also assessed the effect of MgSO4 and cooling on neuromuscular function. RESULTS: Omethoate caused tetanic fade in pig muscles and long-lasting contractions of the motor innervation zone in mouse muscle. Both effects were mitigated, either by i.v. administration of MgSO4 in vivo or by adding 5 mM Mg2+ to the medium bathing isolated preparations. Combination of omethoate and cyclohexanol initially potentiated muscle contractions but then rapidly blocked them. Cyclohexanol alone caused fade and block of muscle contractions in pigs and in isolated preparations. Similar effects were observed ex vivo with cyclohexanone and xylene. Cyclohexanol-induced neuromuscular block was temperature-sensitive and rapidly reversible. CONCLUSIONS: The data indicate a crucial role for organophosphorus and solvent metabolites in muscle weakness following ingestion of agricultural OP insecticide formulations. The metabolites omethoate and cyclohexanol acted conjointly to impair neuromuscular function but their effects were mitigated by elevating extracellular Mg2+ and decreasing core temperature, respectively. Clinical studies of MgSO4 therapy and targeted temperature management in insecticide-poisoned patients are required to determine whether they may be effective adjuncts to treatment.

Plasma cholinesterase activity is influenced by interactive effect between omethoate exposure and CYP2E1 polymorphisms.

The aim of this study was to explore the association between metabolizing enzyme gene polymorphisms and the decrease in cholinesterase activity induced by omethoate exposure. A total of 180 workers exposed to omethoate over an extended period were recruited along with 115 healthy controls. Cholinesterase activity in whole blood, erythrocyte, and plasma was detected using acetylthiocholine and the dithio-bis-(nitrobenzoic acid) method. Six polymorphic loci of GSTT1(+/-), GSTM1(+/-), GSTP1 rs1695, CYP2E1 rs6413432, CYP2E1 rs3813867, and PON2 rs12026 were detected by polymerase chain reaction and restriction fragment length polymorphism (PCR-RFLP). The gene-environment interactions were analyzed using the generalized linear model method. The cholinesterase activity of erythrocyte and plasma in the exposure group was significantly lower than that in the control group (P < 0.001) in general. The plasma cholinesterase activity in the TT + AT genotype in CYP2E1 rs6413432 was lower than that in the AA genotype in the exposure group (P = 0.016). Interaction between the AA genotype in CYP2E1 rs6413432 and omethoate exposure had a significant effect on plasma cholinesterase activity (P = 0.079). The decrease in plasma cholinesterase activity was associated with interaction between the AA genotypes in rs6413432 and omethoate exposure.

Association between genetic polymorphisms of telomere pathway genes and hydrogen peroxide level in omethoate exposure workers.

OBJECTIVE: The aim of this study was to explore the association between genetic variations in telomere pathway genes and the level of hydrogen peroxide (H2O2) in omethoate exposure workers. METHODS: A total of 180 omethoate exposure workers and 115 healthy controls were recruited. The level of H2O2 in plasma was determined with molybdenic acid colorimetry. Polymerase chain reaction and restriction fragment length was used to detect polymorphisms in POT1 rs1034794, POT1 rs10250202, TERF1 rs3863242, and TERT rs2736098. RESULTS: The level of H2O2 in exposure group (4.26 ± 0.71) was significantly higher than that in control group (3.29 ± 0.46). Generalized linear models indicated that risk factors for the increase H2O2 level were exposure [ß(95 % CI) = 0.951 (0.806, 1.096), P < 0.001] and AA + AT genotype in POT1 rs034794 [ß(95 % CI) = 0.397 (0.049, 0.745), P = 0.025]. CONCLUSION: The increase H2O2 level was associated with omethoate exposure and AA + AT genotypes in POT1 gene rs1034794. It provided a new idea that polymorphisms in telomere pathway genes may indirectly regulate telomere length by influencing oxidative stress.

Effect of TRF1 rs3863242 polymorphism on telomere length in omethoate-exposed workers.

Telomere length was found to be associated with omethoate exposure and polymorphisms in certain genes among occupational workers. However, whether the polymorphisms in telomere-binding protein genes influence telomere length remains unclear. To explore the correlation between telomere length and polymorphisms in telomere-binding protein genes, telomere length in peripheral blood leukocytes was determined by real-time quantitative polymerase chain reaction in 180 omethoate-exposed workers and 115 healthy controls. Polymorphisms in 10 pairs of alleles were detected using flight mass spectrometry or polymerase chain reaction-restriction fragment length polymorphism technique. The results showed that individuals with GG genotype in TRF1 rs3863242 had longer telomere lengths than those with AG + AA genotype in the control group (p = 0.005). The multiple regression analysis suggested that both omethoate exposure (b = 0.526, p < 0.001) and TRF1 rs3863242 GG (b = 0.220, p = 0.002) were related to a longer telomere length. In conclusion, GG genotype in TRF1 rs3863242 is linked to prolongation of telomere length, and individuals with GG genotype are recommended to strengthen health protection in a Chinese occupational omethoate-exposed population.

The association between polymorphisms in tankyrase gene and telomere length in omethoate-exposed workers.

Peripheral blood leukocyte telomere length in omethoate-exposed workers is related to environmental exposure and single nucleotide polymorphisms (SNPs) in genes including p21, GSTM1, miR-145, etc. However, the roles of SNPs in tankyrase (TNKS) gene in telomere length are still unknown. The aim of this study was to explore the association between SNPs in TNKS gene and telomere length in omethoate-exposed workers. Telomere length in peripheral blood leukocyte DNA from 180 omethoate-exposed workers and 115 healthy controls was measured using Real-time quantitative polymerase chain reaction (PCR). Genotyping of the selected functional and susceptible SNPs was performed by the flight mass spectrometry based on PCR and single-base extension. The analysis of covariance was performed to find effects of SNPs on telomere length. Generalized linear models were used to analyze the environment, gene, and interaction on telomere length. The results showed that telomere length in the CG + CC genotypes in rs1055328 in TNKS gene was significantly longer than that in the wild homozygous GG genotype both in exposure group (P = 0.017) and in control group (P = 0.038) after adjusting the covariates. The variables kept in the generalized linear models included omethoate-exposure (ß = 0.580, P = 0.001) and rs1055328 (CG + CC) in TNKS gene (ß = 0.339, P = 0.002). The study suggests that the prolongation of telomere length is associated with omethoate-exposure and the CG + CC genotypes in rs1055328 in TNKS gene.

Omethoate induces pharyngeal cancer cell proliferation and G1/S cell cycle progression by activation of Akt/GSK-3ß/cyclin D1 signaling pathway.

Omethoate is a broad category of organophosphorous pesticides (OPs) and has toxic effects on human health under long-term, low-dose exposure. However, the role of omethoate in cancer development remains elusive. The incidence of global head and neck squamous cell carcinomas (HNSCC) has markedly increased in recent years. Thus, we examined whether omethoate induced the proliferation of FaDu cells (a cell line of HNSCC) and if so, what the underlying mechanism was. The study revealed that omethoate induced FaDu cell growth in a dose- and time-dependent manner. Omethoate stimulated FaDu cell proliferation was mainly due to enhancing the G1 to S phase transition by flow cytometry analysis. We also found that omethoate up-regulated cyclin D1, a key gene controlling the G1-S transition. Furthermore, we showed that omethoate was capable of activating the Akt/GSK-3ß signaling pathway. Blockage of Akt by siRNA or small molecule inhibitor significantly suppressed omethoate-induced cyclin D1 expression and cell proliferation. Collectively, these findings demonstrated for the first time that omethoate could induce the pharyngeal cancer cell proliferation by activation of the Akt/GSK-3ß/cyclin D1 signaling pathway.

Telomere length in workers was effected by omethoate exposure and interaction between smoking and p21 polymorphisms.

Omethoate is an organophosphorus pesticide that poses a major health hazard, especially DNA damage. The purpose of this study was to investigate the factors affecting telomere length in workers exposed to omethoate by analyzing the interaction between cell cycle gene polymorphism and environmental factors. The exposure group consisted of 118 workers exposed to omethoate for 8-10 years, the control group comprised 115 healthy people without occupational toxicant exposure history. The telomere length of genomic DNA from peripheral blood leucocyte was determined with real-time PCR. Polymerase chain reaction and restriction fragment length polymorphism was used to detect the polymorphisms in p53, p21 and MDM2 gene. The telomere length in the (CA + AA) genotypes for p21 rs1801270 polymorphism was longer than that in the CC genotype in control group (P = 0.015). The generalized linear model analysis indicated the interaction of the p21 rs1801270 polymorphic (CA + AA) genotypes and smoking has a significant effect on telomere length (ß = -0.258, P = 0.085). The prolongation of telomere length in omethoate-exposed workers was associated with genotypes (CA + AA) of p21 rs1801270, and interactions of (CA + AA) genotypes and smoking factor.

NIR Hyperspectral Imaging Technology Combined with Multivariate Methods to Study the Residues of Different Concentrations of Omethoate on Wheat Grain Surface.

In this study, a hyperspectral imaging system of 866.4-1701.0 nm was selected and combined with multivariate methods to identify wheat kernels with different concentrations of omethoate on the surface. In order to obtain the optimal model combination, three preprocessing methods (standard normal variate (SNV), Savitzky-Golay first derivative (SG1), and multivariate scatter correction (MSC)), three feature extraction algorithms (successive projections algorithm (SPA), random frog (RF), and neighborhood component analysis (NCA)), and three classifier models (decision tree (DT), k-nearest neighbor (KNN), and support vector machine (SVM)) were applied to make a comparison. Firstly, based on the full wavelengths modeling analysis, it was found that the spectral data after MSC processing performed best in the three classifier models. Secondly, three feature extraction algorithms were used to extract the feature wavelength of MSC processed data and based on feature wavelengths modeling analysis. As a result, the MSC-NCA-SVM model performed best and was selected as the best model. Finally, in order to verify the reliability of the selected model, the hyperspectral image was substituted into the MSC-NCA-SVM model and the object-wise method was used to visualize the image classification. The overall classification accuracy of the four types of wheat kernels reached 98.75%, which indicates that the selected model is reliable.

Identification and Dissipation of Omethoate and Its Main Metabolite DMP in Wheat Determined by UPLC-QTOF/MS.

A study was carried out to evaluate the dissipation kinetics of field-applied omethoate during wheat storage. Both the identification and metabolic dynamics of omethoate metabolites were analyzed using UPLC-QTOF/MS. The presence of the metabolite dimethyl phosphate (DMP) was confirmed in wheat samples with applied omethoate. This might be because the group attached to the P atom of omethoate is replaced by a hydroxyl group through hydrolysis, thus leading to the formation of the specific metabolite DMP during wheat storage. Although the initial concentrations of DMP in different doses were considerably lower than those of omethoate, the half-life values of DMP were 11.87-31.50 days, which were close to the half-life of the parent omethoate (11.85-30.94 days). This indicates that potential health risks might be caused by dietary exposure to DMP and omethoate. Therefore, more importance should be given to the risk assessment for omethoate and its metabolite DMP in wheat.

Association of genetic polymorphisms of miR-145 gene with telomere length in omethoate-exposed workers.

Omethoate, an organophosphorous pesticide, causes a variety of health effects, especially the damage of chromosome DNA. The aim of the study was to assess the correlation between polymorphisms of encoding miRNA genes and telomere length in omethoate-exposure workers. 180 workers with more than 8 years omethoate-exposure and 115 healthy controls were recruited in the study. Genotyping for the selected single nucleotide polymorphisms loci were performed using the flight mass spectrometry. Real-time fluorescent quantitative polymerase chain reaction(PCR) method was applied to determine the relative telomere length(RTL) in human peripheral blood leukocytes DNA. After adjusting the covariate of affecting RTL, covariance analysis showed that the female was significantly longer than that of the male in control group(P < 0.046). For the miR-145 rs353291 locus, this study showed that RTL of mutation homozygous AG+GG individuals was longer than that of wild homozygous AA in the exposure group (P = 0.039). In the control group, RTL with wild homozygous TT genotype in miR-30a rs2222722 polymorphism locus was longer than that of the mutation homozygous CC genotype (P = 0.038). After multiple linear regression analysis, the independent variables of entering into the model were omethoate-exposure (b = 0.562, P < 0.001), miR-145 rs353291 (AG+GG) (b = 0.205, P = 0.010). The prolongation of relative telomere length in omethoate exposed workers was associated with AG+GG genotypes in rs353291 polymorphism of encoding miR-145 gene.

Telomere Length in Workers Was Effected by Omethoate Exposure, GSTM1 Deletion, Interaction Between Smoking and GSTP1 Polymorphisms.

OBJECTIVE: The aim of this study was to explore the association between telomere length and metabolizing enzyme gene polymorphisms and environmental factors in omethoate-exposed workers. METHODS: The gene-environment interactions were analyzed with generalized linear model method. RESULTS: The relative telomere lengths in the individuals with GSTM1-deletion were longer than that in non-deletion genotype in the control group (P = 0.011); the relative telomere lengths with GG+AG genotypes in GSTP1 rs1695 were longer than that of AA genotype in the exposure group (P = 0.039). The interaction between the GG+AG genotypes in GSTP1 rs1695 and smoking exposure had significant effect on telomere length (P < 0.05). CONCLUSIONS: The prolongation of relative telomere length in omethoate-exposed workers was associated with GSTM1-deletion, GG+AG genotypes, and interactions of GG+AG genotypes and smoking factor.