Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework...Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework(M-COF)adsorbent for the magnetic solid-phase extraction(MSPE)of OPPs from foods was reported.M-COF was synthesized by the Schiff base condensation reaction of 1,3,5-tris(4-aminophenyl)benzene and 4,4-biphenyldicarboxaldehyde on the surface of amino-functionalized magnetic nanoparticles.Density functional theory(DFT)calculations showed that adsorption of OPPs onto the surface of M-COF involved hydrophobic effects,van der Waals interactions,π-πinteractions,halogen-N bonding,and hydrogen bonding.Combined with gas chromatography-mass spectrometry(GC-MS)technology,the MSPE method features low limits of detection for OPPs(0.002-0.015μg/L),good reproducibility(1.45%-6.14%),wide linear detection range(0.01-1μg/L,R≥0.9935),and satisfactory recoveries(87.3%-110.4%).The method was successfully applied for the trace analysis of OPPs in spiked fruit juices.展开更多
Biomimetic nanozymes opens up new opportunities for sensitive,rapid and field detection of organophosphorus pesticides(OPs).However,it still remains challenges in how to improve the sensitivity and stability of biomim...Biomimetic nanozymes opens up new opportunities for sensitive,rapid and field detection of organophosphorus pesticides(OPs).However,it still remains challenges in how to improve the sensitivity and stability of biomimetic nanozymes under harsh conditions.Herein,we synthesized a novel biomimetic nanozyme composed of hemin and bovine serum albumin(BSA)in the nanopores of poly-l-lysine methacryloyl(PLMA)inverse opal hydrogel(PLMA-Hemin-BSA).PLMA-Hemin-BSA achieves superior peroxidase-like activity and shows high stability due to the confinement effect.A multi-enzyme cascade reaction was constructed for the colorimetric detection of five widely used OPs by integrating PLMAHemin-BSA with natural choline oxidase and acetylcholinesterase.The detection limits for dichlorvos,chlorpyrifos,paraoxon,methamidophos,and parathion were as low as 0.024,0.073,0.12,0.56,and 1.4 ng/mL,respectively.More importantly,the average recovery rates and the relative standard deviations(RSD)of chlorpyrifos in paddy water,soil and wheat samples were 86.62%-100.13%and 2.08%-8.65%,which meet the standard of the International Union of Pure and Applied Chemistry(IUPAC,recoveries of 70%-120%with RSD<20%).This study represented advanced methods toward enhancing the activity and stability of biomimetic nanozymes via spatial nanopores-assisted strategy.展开更多
AIM:To investigate the associations between urinary dialkyl phosphate(DAP)metabolites of organophosphorus pesticides(OPPs)exposure and age-related macular degeneration(AMD)risk.METHODS:Participants were drawn from the...AIM:To investigate the associations between urinary dialkyl phosphate(DAP)metabolites of organophosphorus pesticides(OPPs)exposure and age-related macular degeneration(AMD)risk.METHODS:Participants were drawn from the National Health and Nutrition Examination Survey(NHANES)between 2005 and 2008.Urinary DAP metabolites were used to construct a machine learning(ML)model for AMD prediction.Several interpretability pipelines,including permutation feature importance(PFI),partial dependence plot(PDP),and SHapley Additive exPlanations(SHAP)analyses were employed to analyze the influence from exposure features to prediction outcomes.RESULTS:A total of 1845 participants were included and 137 were diagnosed with AMD.Receiver operating characteristic curve(ROC)analysis evaluated Random Forests(RF)as the best ML model with its optimal predictive performance among eleven models.PFI and SHAP analyses illustrated that DAP metabolites were of significant contribution weights in AMD risk prediction,higher than most of the socio-demographic covariates.Shapley values and waterfall plots of randomly selected AMD individuals emphasized the predictive capacity of ML with high accuracy and sensitivity in each case.The relationships and interactions visualized by graphical plots and supported by statistical measures demonstrated the indispensable impacts from six DAP metabolites to the prediction of AMD risk.CONCLUSION:Urinary DAP metabolites of OPPs exposure are associated with AMD risk and ML algorithms show the excellent generalizability and differentiability in the course of AMD risk prediction.展开更多
[Objectives]This study was conducted to purify mutton samples by gel permeation chromatography(GPC).[Methods]Fourteen organophosphorus pesticide residues in samples were qualitatively and quantitatively analyzed by ga...[Objectives]This study was conducted to purify mutton samples by gel permeation chromatography(GPC).[Methods]Fourteen organophosphorus pesticide residues in samples were qualitatively and quantitatively analyzed by gas chromatography-mass spectrometry(GC-MS)in selective ion scanning mode(SIM).[Results]The organophosphorus pesticide standard solutions showed good linearity in the mass concentration range of 0.1-10.0μg/ml with correlation coefficients(r)not lower than 0.999,and the detection limits(S=3 N)ranged from 0.01 to 0.05 mg/kg.The average recovery values were in the range of 80.2%-99.7%,with relative standard deviations(RSDs,n=3)in the range of 1.8%-6.3%,at the addition levels of 0.5,1.0 and 2.0 mg/kg.[Conclusions]The method is simple,sensitive and accurate,and can be used for the determination of organophosphorus pesticide residues in mutton.展开更多
Objective:To analyze the efficacy of reduced glutathione(GSH)in the emergency treatment of patients with organophosphorus pesticide poisoning(AOPP).Methods:A total of 100 AOPP patients admitted to the emergency depart...Objective:To analyze the efficacy of reduced glutathione(GSH)in the emergency treatment of patients with organophosphorus pesticide poisoning(AOPP).Methods:A total of 100 AOPP patients admitted to the emergency department between January 2022 and January 2024 were selected and randomly divided into two groups.The observation group(n=50)received GSH combined with conventional treatment,while the reference group(n=50)received conventional treatment alone.The overall treatment efficacy,serum indicators,and adverse reaction rates were compared.Results:The observation group exhibited a higher overall treatment efficacy compared to the reference group(P<0.05).Post-treatment,serum indicator levels in the observation group were lower than those in the reference group,and the adverse reaction rate was also lower in the observation group(P<0.05).Conclusion:GSH can improve the overall treatment efficacy in AOPP patients,protect liver function,reduce inflammatory responses in the body,and minimize post-treatment adverse effects,thus accelerating recovery and demonstrating significant therapeutic advantages.展开更多
The uncertainty of standard solution plays an important role in detection of pesticide residues. It may affect the accuracy of detection results. In this study, the 14 organophosphorus pesticides mixed standard soluti...The uncertainty of standard solution plays an important role in detection of pesticide residues. It may affect the accuracy of detection results. In this study, the 14 organophosphorus pesticides mixed standard solution was used as the material to analyze all the influencing factors for the preparation of mixed standard solution with uncertainty as the only judging index. The preparation uncertainty of mixed standard solution was calculated with the top-down calculation method. In the end, the expanded uncertainty was presented. The results showed that the preparation of mixed standard solution from stock solution with precise pipettes had a relatively low uncertainty.展开更多
We reviewed organophosphorus pesticide use in Japan between 1982 and 2016 using data from the National Institute of Environmental Studies. Organophosphorus pesticide concentrations in river water throughout Japan were...We reviewed organophosphorus pesticide use in Japan between 1982 and 2016 using data from the National Institute of Environmental Studies. Organophosphorus pesticide concentrations in river water throughout Japan were taken from the literature, and risk assessments were performed for some organophosphorus pesticides based on risk quotients and hazard quotients. Assessments were performed for 20 common pesticides,including insecticides, fungicides, and herbicides. The amounts used decreased in the order: insecticides > herbicides > fungicides. Organophosphorus insecticide and fungicide use have decreased over the last four decades, but organophosphorus herbicide use has increased. During this period, annual organophosphorus pesticide use was the highest for chlorpyrifos(105,263 tons/year) and the lowest for glyphosate-sodium(8 tons/year). The ecotoxicological risk assessment indicated that diazinon and fenitrothion posed strong risks to the Japanese aquatic environment, and chlorpyrifos and malathion have moderate risks. None of the pesticides that were assessed posed significant risks to humans.Continued use of organophosphorus pesticides in Japan may cause strong risks to aquatic environments. These risks should be reassessed periodically.展开更多
BACKGROUND:Penehyclidine is a newly developed anticholinergic agent.We aimed to investigate the role of penehyclidine in acute organophosphorus pesticide poisoning(OP)patients.METHODS:We searched the Pubmed,Cochrane l...BACKGROUND:Penehyclidine is a newly developed anticholinergic agent.We aimed to investigate the role of penehyclidine in acute organophosphorus pesticide poisoning(OP)patients.METHODS:We searched the Pubmed,Cochrane library,EMBASE,Chinese National Knowledge Infrastructure(CNKI),Chinese Biomedical literature(CBM)and Wanfang databases.Randomized controlled trials(RCTs)recruiting acute OP patients were identifi ed for meta-analysis.Main outcomes included cure rate,mortality rate,time to atropinization,time to 60%normal acetylcholinesterase(AchE)level,rate of intermediate syndrome(IMS)and rate of adverse drug reactions(ADR).RESULTS:Sixteen RCTs involving 1,334 patients were identifi ed.Compared with the atropineor penehyclidine-alone groups,atropine combined with penehyclidine significantly increased the cure rate(penehyclidine+atropine vs.atropine,0.97 vs.0.86,RR 1.13,95%CI[1.07–1.19];penehyclidine+atropine vs.penehyclidine,0.93 vs.0.80,RR 1.08,95%CI[1.01–1.15])and reduced the mortality rate(penehyclidine+atropine vs.atropine,0.015 vs.0.11,RR 0.17,95%CI[0.06–0.49];penehyclidine+atropine vs.penehyclidine,0.13 vs.0.08,RR 0.23,95%CI[0.04–1.28]).Atropine combined with penehyclidine in OP patients also helped reduce the time to atropinization and AchE recovery,the rate of IMS and the rate of ADR.Compared with a single dose of atropine,a single dose of penehyclidine also signifi cantly elevated the cure rate,reduced times to atropinization,AchE recovery,and rate of IMS.CONCLUSION:Atropine combined with penehyclidine benefi ts OP patients by enhancing the cure rate,mortality rate,time to atropinization,AchE recovery,IMS rate,total ADR and duration of hospitalization.Penehyclidine combined with atropine is likely a better initial therapy for OP patients than atropine alone.展开更多
Two procedures were compared for extraction and clean-up of 20organophosphorus and 19 pyrethroid pesticides in sediment to identify the more effective procedurefor groups of pesticides or individual compounds. In Proc...Two procedures were compared for extraction and clean-up of 20organophosphorus and 19 pyrethroid pesticides in sediment to identify the more effective procedurefor groups of pesticides or individual compounds. In Procedure I, methanol/water and n-hexane wereused for extraction, and 1:10 (v/v) dichloromethane in n-hexane and acetone were used as eluents foreluting the analyte through the cartridge, with one evaporating steps on a rotary evaporator andtwo eluting steps on the cartridge. n-hexane/acetone (2:1, v/v) was used for extraction and elutionin Procedure II with one evaporating step on a rotary evaporator and one eluting step on thecartridge. All extractions were performed under an ultrasonic bath and gas chromatography and massspectrometry were utilized for measurements. Procedure II was developed as a rapid, timesaving, lesscostly and safer substitute for Procedure I which was an old method. Procedure II was moreeffective for almost all the organophosphorus pesticides tested and 11of the 19 pyrethroidpesticides, while Procedure I was more appropriate for analysis of 5 pyrethroid pesticides. However,recoveries of most pyrethroid pesticides were fairly low. Thus, further studies should focus onadjustment and formulation of solvents for more efficient extraction and clean-up of pyrethroidpesticides from sediment samples.展开更多
The plant cellulose powder was activated by two different methods using 1,4-butanediol diglycidyl ether(BTDE)and 1,1′-Carbonyldiimidazole(CDI) as the chemical coupling agents.Organophosphorus hydrolase(OPH) from Flav...The plant cellulose powder was activated by two different methods using 1,4-butanediol diglycidyl ether(BTDE)and 1,1′-Carbonyldiimidazole(CDI) as the chemical coupling agents.Organophosphorus hydrolase(OPH) from Flavobacterium ATCC 27551 was immobilized on any of activated support through covalent bonding.The optimal conditions of affecting parameters on enzyme immobilization in both methods were found, and it was demonstrated that the highest activity yields of immobilized OPH onto epoxy and CDI treated cellulose were 68.32%and 73.51%, respectively.The surface treatment of cellulose via covalent coupling with BTDE and CDI agents was proved by FTIR analysis.The kinetic constants of the free and immobilized enzymes were determined, and it was showed that both immobilization techniques moderately increased the Kmvalue of the free OPH.The improvements in storage and thermal stability were investigated and depicted that the half-life of immobilized OPH over the surface of epoxy modified cellulose had a better growth compared to the free and immobilized enzymes onto CDI treated support.Also, the pH stability of the immobilized preparations was enhanced relative to the free counterpart and revealed that all enzyme samples would have the same optimum pH value for stability at 9.0.Additionally, the immobilized OPH onto epoxy and CDI activated cellulose retained about 59% and 68% of their initial activity after ten turns of batch operation, respectively.The results demonstrated the high performance of OPH enzyme in immobilized state onto an inexpensive support with the potential of industrial applications.展开更多
Organophosphorus pesticides(OPPs) are a set of toxic persistent organic pollutants(POPs) present in the environment. Recently, biochar-mediated bioremediation has exhibited many advantages over conventional methods fo...Organophosphorus pesticides(OPPs) are a set of toxic persistent organic pollutants(POPs) present in the environment. Recently, biochar-mediated bioremediation has exhibited many advantages over conventional methods for the remediation of pesticide-contaminated soil. In the present study, biochar and nitrogen fertilizer(NH_4NO_3)were employed to remediate OPP-contaminated soil and the greenhouse gas(GHG) emission during 90 days of incubation was investigated. After thermal desorption treatment, the content of organophosphorus pesticides reduced from 175.61 μg·kg^(-1) to 62.68 μg·kg^(-1). The addition of NH_4NO_3 in the following bioremediation led to larger reduction(34.35%) of the pesticide concentration than that of biochar(31.90%) for the contaminated soils with thermal desorption treatment, while the simultaneous addition of biochar and NH_4NO_3 led to the largest reduction of pesticide concentration(11.07%) for the soil without thermal desorption treatment. The addition of biochar and NH_4NO_3 only slightly increased the emission rate of GHGs from the soil without thermal treatment,but remarkably increased the emission rate of GHGs from the soil after thermal treatment. In most cases, the addition of NH_4NO_3 is more effective than biochar to promote the degradation of pesticide, but also exhibited higher GHG emission. The microbial community analysis suggests that the enhanced degradation of pesticide is mainly owing to the increased activity of microorganism.展开更多
The widespread use of organophosphorus pesticides(OPs) poses a great threat to human health and has made the detection of OP residues in food an important task,especially in view of the fact that easy and rapid detect...The widespread use of organophosphorus pesticides(OPs) poses a great threat to human health and has made the detection of OP residues in food an important task,especially in view of the fact that easy and rapid detection methods are needed.Because OPs have inhibitory effects on the activity of α-naphthyl acetate esterase(ANAE) in plants,in this work we evaluated the possibility of detecting OPs in vegetables with ANAE extracted from commercial flour.The limits of detection(LODs) obtained for methamidophos,dichlorvos,phoxim,dimethoate,and malathion in lettuce samples with crude ANAE were 0.17,0.11,0.11,0.96,and 1.70 mg/kg,respectively.Based on the maximum residue limits(MRLs) for OPs in food stipulated by Chinese laws which are 0.05,0.20,0.05,1.00,and 8.00 mg/kg for methamidophos,dichlorvos,phoxim,dimethoate,and malathion,respectively,the esterase inhibition method with crude ANAE had sufficient sensitivity to detect the residues of dichlorvos,dimethoate,and malathion in lettuce,but it could not be used to guarantee the safety of the same samples if methamidophos or phoxim residue was present.The sensitivity of the method was improved by the use of esterase purified by ammonium sulfate salting-out.The LODs obtained for methamidophos and phoxim with purified esterase were lower than the MRLs for these OPs in food.This is a very promising method for the detection of OP residues in vegetables using crude or purified esterase because of its cheapness,sensitivity,and convenience.展开更多
The objectives of this study were to optimize instrumental parameters and conditions for analysis of selected organop- hosphorus pesticides (OPPs) by gas chromatography (GC) with nitrogen-phosphorus detection (NPD) (G...The objectives of this study were to optimize instrumental parameters and conditions for analysis of selected organop- hosphorus pesticides (OPPs) by gas chromatography (GC) with nitrogen-phosphorus detection (NPD) (GC-NPD); to select an appropriate solvent system; to conduct a comparison of sonication and shaking extractions; and to select an appropriate procedure for extracting organophosphorus pesticides from soils. Procedure I consisted of n-hexane or petroleum ether together with acetone used as solvents, while Procedure contained several solvents including acetone, methanol, dichloromethane, and n-hexane or petroleum ether. Experimental results indicated that a mixture of petroleum ether/acetone (2:1, v/v) could be used in place of n-hexane/acetone (2:1, v/v) as it was a less expensive solvent system. In addition, shaking under a water bath at 20 °C was more effective than sonication. Also, Procedure I was more effective, safer, and more timesaving than Procedure Procedure I was applied to three soil types of different organic matter content, with recoveries of the OPPs from the yellow-brown soils, which had a higher organic matter content, being lower than those from the yellow and red soils.展开更多
Pesticides have the potential to leave harmful effects on humans, animals, other living organisms, and the environment. Several human metabolic proteins inhibited after exposure to organophosphorus pesticides absorbed...Pesticides have the potential to leave harmful effects on humans, animals, other living organisms, and the environment. Several human metabolic proteins inhibited after exposure to organophosphorus pesticides absorbed through the skin, inhalation, eyes and oral mucosa, are most important targets for this interaction study. The crystal structure of five different proteins, PDBIDs: 3LII, 3NXU, 4GTU, 2XJ1 and 1YXA in Homo sapiens (H. sapiens), interact with organophosphorus pesticides at the molecular level. The 3-D structures were found to be of good quality and validated through PROCHECK, ERRAT and ProSA servers. The results show that the binding energy is maximum -45.21 relative units of cytochrome P450 protein with phosmet pesticide. In terms of H-bonding, methyl parathion and parathion with acetylcholinesterase protein, parathion, methylparathion and phosmet with protein kinase C show the highest interaction. We conclude that these organophosphorus pesticides are more toxic and inhibit enzymatic activity by interrupting the metabolic pathways in H. sapiens.展开更多
In order to obtain high-efficiency organophosphorus solubilizing bacteria, 21 strains of organophosphate solubilizing bacteria were isolated from the rhizosphere soil of Camellia oleifera plants, and the transparent c...In order to obtain high-efficiency organophosphorus solubilizing bacteria, 21 strains of organophosphate solubilizing bacteria were isolated from the rhizosphere soil of Camellia oleifera plants, and the transparent circle method was used for rescreening. Only 4 strains of bacteria could form transparent circle on organophosphorus medium. The D/d value of 4 strains of bacteria was between 1.62 and 2.71, among which the D/d value of strain Y6 was the highest(2.71). The available phosphorus content of the fermentation supernatant was 8.50~14.79 mg/L, which was 7.88~14.17 mg/L higher than that of CK. The strain Y6 had the highest soluble phosphorus content of 14.79 mg/L in the fermentation supernatant, which was 14.17 mg/L higher than that of CK. According to the colony morphology, physiological and biochemical characteristics and 16S rDNA sequence analysis of strain Y6, it is preliminarily determined that strain Y6 is Pseudomonas. Strain Y6 is beneficial to improve the supply of phosphorus in rhizosphere soil of Camellia oleifera and promote the growth of Camellia oleifera. It has great potential in the development of bio-organic fertilizer.展开更多
[Objectives ] The paper was to explore enzyme inhibition rate method for rapid detection of organophosphorus and carbamate pesticides in cowpea. [ Methods ] Acetylcholinesterase (ACHE) was added to cowpea extract, t...[Objectives ] The paper was to explore enzyme inhibition rate method for rapid detection of organophosphorus and carbamate pesticides in cowpea. [ Methods ] Acetylcholinesterase (ACHE) was added to cowpea extract, to determine the inhibition rate of extract against enzyme. The influences of different sampiing methods and sampling parts on detection results were compared. [ Results] The positive rate of standard sampling was 18.18% higher than that of non-stand- ard sampling, and the positive rate of samples collected from cowpea tail was 16.67% higher than that collected from other parts. [ Condmions] Enzyme inhibi- tion rate method is suitable for rapid detection of organophosphorus and carbamate pesticides in cowpea.展开更多
[ Objectives] This study was conducted to establish a QuEChERS-gas chromatography method for determination of eight kinds of organophosphorus pesticide residues in pepper. [Methods] The samples were extracted by aceto...[ Objectives] This study was conducted to establish a QuEChERS-gas chromatography method for determination of eight kinds of organophosphorus pesticide residues in pepper. [Methods] The samples were extracted by acetonitrile, and anhydrous magnesium sulfate was used for salting out. The extracts were then purified by dispersive solid phase extraction combining with GCB, C18 and PSA. Samples were analyzed by FPD detector. External standard was used as quantitive method. [ Results] The detection limits were in the range of 0. 001 -0. 008 mg/kg, the average recoveries ranged from 83.5% to 101.2% , and the relative standard deviation (RSD) of the eight organophosphorus pesticide residues were below 5%. [ Conclusions] The method is simple, quick, easy and effective for the determination of pepper.展开更多
To examine a) the effect of organophosphorus pesticide exposure on activity of carboxylic esterases, namely butyrylcholinesterase (BChE), carboxylesterase (CarbE) and paraoxonase (PonE); and b) the association...To examine a) the effect of organophosphorus pesticide exposure on activity of carboxylic esterases, namely butyrylcholinesterase (BChE), carboxylesterase (CarbE) and paraoxonase (PonE); and b) the association of polymorphisms of BChE and PonE with individual genetic susceptibility to organophosphorus pesticide exposure. Methods A cross-sectional study was conducted in 75 workers exposed to organophosphorus pesticides and 100 non-exposed controls. The serum activity of these enzymes was measured. Variant forms of BCHE-K, PON-192, and PON-55 were detected. A symptom score was developed as a proxy measure of clinical outcomes. Results Activities of both BChE and CarbE were lower in exposed workers (27.3±21.65 runol.hl.mL^-l and 235.6±104.03 nmol-min^-l.mL^-l) than in non-exposed workers (78.313±30.354 nmol.h^-l.mL^-1 and 362.681_+194.997 nmol.min^-1.mL^-1). The activity of PonE was not associated with exposure status. The AChE activity in the exposed workers with BCHE-K genotype UU (61 cases), genotype UK (12 cases) and genotype KK (2 cases) was 105.05, 84.42 and 79.00 mmol-h^-1.mL^-1, respectively and the accumulative symptom scores were 3.74, 9.17, and 12.50 accordingly. The AChE activity in the exposed workers with PON-192 genotype BB (37), genotype AB (27) and genotype AA (11) was 116.8, 91.2, and 72,3 mmol-h^-1.mL^-1, respectively and the symptom scores were 2.00, 6.74, and 9.73 accordingly. The AChE activity in those with PON-55 genotype LL (70) and genotype LM (5) was 102.4 and 82.8 mmol-h^-1.mL^-1 and the symptom scores were 4.53 and 9.20. The symptom score was the highest in individuals with abnormal homozygote for each of the three gene loci. Condusions Long-term exposure to organophosphorus pesticides can inhibit BChE and CarbE activity, but exerts no inhibitory effect on PonE activity. Different genotypes of BCHE-K, PON-192, and PON-55 may be related to the severity of adverse health effects of organophosphorus pesticide exposure. Implications of potentially higher susceptibility of workers with mutant homozygotes should be evaluated to reduce health risks.展开更多
We constructed an expression cassette of the organophosphorus pesticide degrading(opal)gene under the control of the E8 promoter.Then opd was transformed into tomato fruit using an agroinfiltration transient expressio...We constructed an expression cassette of the organophosphorus pesticide degrading(opal)gene under the control of the E8 promoter.Then opd was transformed into tomato fruit using an agroinfiltration transient expression system.β-Glucuronidase(GUS)staining,reverse transcription-polymerase chain reaction(RT-PCR),wavelength scanning,and fluorescent reaction were performed to examine the expression of the opd gene and the hydrolysis activity on coumaphos of organo-phosphorus hydrolase(OPH)in tomato fruit.The results show that the agroinfiltrated tomato fruit-expressed OPH had the maximum hydrolysis activity of about 11.59 Uhng total soluble protein.These results will allow us to focus on breeding transgenic plants that could not only enhance the degrading capability of fruit and but also hold no negative effects on pest control when spraying organophosphorus pesticides onto the seedlings in fields.展开更多
基金supported by Key Research and Development Project of Shandong Province(2021ZDSYS12)National Natural Science Foundation of China(22076086,21777089)+3 种基金Taishan Scholar Program of Shandong Province(ts20190948)Shandong Province Science and Technology Small and Medium Enterprises Innovation Ability Enhancement Project(2023TSGC0689,2023TSGC0055)Natural Science Foundation of Shandong Province(ZR2021MB086,ZR2023QB035)Jinan City University and Institute Innovation Team Project(2021GXRC061,20228045,202333027)。
文摘Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework(M-COF)adsorbent for the magnetic solid-phase extraction(MSPE)of OPPs from foods was reported.M-COF was synthesized by the Schiff base condensation reaction of 1,3,5-tris(4-aminophenyl)benzene and 4,4-biphenyldicarboxaldehyde on the surface of amino-functionalized magnetic nanoparticles.Density functional theory(DFT)calculations showed that adsorption of OPPs onto the surface of M-COF involved hydrophobic effects,van der Waals interactions,π-πinteractions,halogen-N bonding,and hydrogen bonding.Combined with gas chromatography-mass spectrometry(GC-MS)technology,the MSPE method features low limits of detection for OPPs(0.002-0.015μg/L),good reproducibility(1.45%-6.14%),wide linear detection range(0.01-1μg/L,R≥0.9935),and satisfactory recoveries(87.3%-110.4%).The method was successfully applied for the trace analysis of OPPs in spiked fruit juices.
基金supported by the National Natural Science Foundation of China(Nos.22125606 and 22241604)Chinese Academy of Sciences Project for Young Scientists in Basic Research(No.YSBR-086)+1 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(No.XBD0750000)the Research Start-up Funding Project of Kashi University(No.GCC2024ZK-014)。
文摘Biomimetic nanozymes opens up new opportunities for sensitive,rapid and field detection of organophosphorus pesticides(OPs).However,it still remains challenges in how to improve the sensitivity and stability of biomimetic nanozymes under harsh conditions.Herein,we synthesized a novel biomimetic nanozyme composed of hemin and bovine serum albumin(BSA)in the nanopores of poly-l-lysine methacryloyl(PLMA)inverse opal hydrogel(PLMA-Hemin-BSA).PLMA-Hemin-BSA achieves superior peroxidase-like activity and shows high stability due to the confinement effect.A multi-enzyme cascade reaction was constructed for the colorimetric detection of five widely used OPs by integrating PLMAHemin-BSA with natural choline oxidase and acetylcholinesterase.The detection limits for dichlorvos,chlorpyrifos,paraoxon,methamidophos,and parathion were as low as 0.024,0.073,0.12,0.56,and 1.4 ng/mL,respectively.More importantly,the average recovery rates and the relative standard deviations(RSD)of chlorpyrifos in paddy water,soil and wheat samples were 86.62%-100.13%and 2.08%-8.65%,which meet the standard of the International Union of Pure and Applied Chemistry(IUPAC,recoveries of 70%-120%with RSD<20%).This study represented advanced methods toward enhancing the activity and stability of biomimetic nanozymes via spatial nanopores-assisted strategy.
基金Supported by the National Key Research and Development Program of China(No.2022YFC2502800)the National Natural Science Foundation of China(No.82171076)the Shanghai Municipal Education Commission(No.2023KJ05-67).
文摘AIM:To investigate the associations between urinary dialkyl phosphate(DAP)metabolites of organophosphorus pesticides(OPPs)exposure and age-related macular degeneration(AMD)risk.METHODS:Participants were drawn from the National Health and Nutrition Examination Survey(NHANES)between 2005 and 2008.Urinary DAP metabolites were used to construct a machine learning(ML)model for AMD prediction.Several interpretability pipelines,including permutation feature importance(PFI),partial dependence plot(PDP),and SHapley Additive exPlanations(SHAP)analyses were employed to analyze the influence from exposure features to prediction outcomes.RESULTS:A total of 1845 participants were included and 137 were diagnosed with AMD.Receiver operating characteristic curve(ROC)analysis evaluated Random Forests(RF)as the best ML model with its optimal predictive performance among eleven models.PFI and SHAP analyses illustrated that DAP metabolites were of significant contribution weights in AMD risk prediction,higher than most of the socio-demographic covariates.Shapley values and waterfall plots of randomly selected AMD individuals emphasized the predictive capacity of ML with high accuracy and sensitivity in each case.The relationships and interactions visualized by graphical plots and supported by statistical measures demonstrated the indispensable impacts from six DAP metabolites to the prediction of AMD risk.CONCLUSION:Urinary DAP metabolites of OPPs exposure are associated with AMD risk and ML algorithms show the excellent generalizability and differentiability in the course of AMD risk prediction.
基金Supported by The Fourth Batch of High-end Talent Project in Hebei Province.
文摘[Objectives]This study was conducted to purify mutton samples by gel permeation chromatography(GPC).[Methods]Fourteen organophosphorus pesticide residues in samples were qualitatively and quantitatively analyzed by gas chromatography-mass spectrometry(GC-MS)in selective ion scanning mode(SIM).[Results]The organophosphorus pesticide standard solutions showed good linearity in the mass concentration range of 0.1-10.0μg/ml with correlation coefficients(r)not lower than 0.999,and the detection limits(S=3 N)ranged from 0.01 to 0.05 mg/kg.The average recovery values were in the range of 80.2%-99.7%,with relative standard deviations(RSDs,n=3)in the range of 1.8%-6.3%,at the addition levels of 0.5,1.0 and 2.0 mg/kg.[Conclusions]The method is simple,sensitive and accurate,and can be used for the determination of organophosphorus pesticide residues in mutton.
文摘Objective:To analyze the efficacy of reduced glutathione(GSH)in the emergency treatment of patients with organophosphorus pesticide poisoning(AOPP).Methods:A total of 100 AOPP patients admitted to the emergency department between January 2022 and January 2024 were selected and randomly divided into two groups.The observation group(n=50)received GSH combined with conventional treatment,while the reference group(n=50)received conventional treatment alone.The overall treatment efficacy,serum indicators,and adverse reaction rates were compared.Results:The observation group exhibited a higher overall treatment efficacy compared to the reference group(P<0.05).Post-treatment,serum indicator levels in the observation group were lower than those in the reference group,and the adverse reaction rate was also lower in the observation group(P<0.05).Conclusion:GSH can improve the overall treatment efficacy in AOPP patients,protect liver function,reduce inflammatory responses in the body,and minimize post-treatment adverse effects,thus accelerating recovery and demonstrating significant therapeutic advantages.
文摘The uncertainty of standard solution plays an important role in detection of pesticide residues. It may affect the accuracy of detection results. In this study, the 14 organophosphorus pesticides mixed standard solution was used as the material to analyze all the influencing factors for the preparation of mixed standard solution with uncertainty as the only judging index. The preparation uncertainty of mixed standard solution was calculated with the top-down calculation method. In the end, the expanded uncertainty was presented. The results showed that the preparation of mixed standard solution from stock solution with precise pipettes had a relatively low uncertainty.
基金The Japan Society for the Promotion of Science(JSPS)supported by JSPS KAKENHI grant number16KT0149,Japan
文摘We reviewed organophosphorus pesticide use in Japan between 1982 and 2016 using data from the National Institute of Environmental Studies. Organophosphorus pesticide concentrations in river water throughout Japan were taken from the literature, and risk assessments were performed for some organophosphorus pesticides based on risk quotients and hazard quotients. Assessments were performed for 20 common pesticides,including insecticides, fungicides, and herbicides. The amounts used decreased in the order: insecticides > herbicides > fungicides. Organophosphorus insecticide and fungicide use have decreased over the last four decades, but organophosphorus herbicide use has increased. During this period, annual organophosphorus pesticide use was the highest for chlorpyrifos(105,263 tons/year) and the lowest for glyphosate-sodium(8 tons/year). The ecotoxicological risk assessment indicated that diazinon and fenitrothion posed strong risks to the Japanese aquatic environment, and chlorpyrifos and malathion have moderate risks. None of the pesticides that were assessed posed significant risks to humans.Continued use of organophosphorus pesticides in Japan may cause strong risks to aquatic environments. These risks should be reassessed periodically.
文摘BACKGROUND:Penehyclidine is a newly developed anticholinergic agent.We aimed to investigate the role of penehyclidine in acute organophosphorus pesticide poisoning(OP)patients.METHODS:We searched the Pubmed,Cochrane library,EMBASE,Chinese National Knowledge Infrastructure(CNKI),Chinese Biomedical literature(CBM)and Wanfang databases.Randomized controlled trials(RCTs)recruiting acute OP patients were identifi ed for meta-analysis.Main outcomes included cure rate,mortality rate,time to atropinization,time to 60%normal acetylcholinesterase(AchE)level,rate of intermediate syndrome(IMS)and rate of adverse drug reactions(ADR).RESULTS:Sixteen RCTs involving 1,334 patients were identifi ed.Compared with the atropineor penehyclidine-alone groups,atropine combined with penehyclidine significantly increased the cure rate(penehyclidine+atropine vs.atropine,0.97 vs.0.86,RR 1.13,95%CI[1.07–1.19];penehyclidine+atropine vs.penehyclidine,0.93 vs.0.80,RR 1.08,95%CI[1.01–1.15])and reduced the mortality rate(penehyclidine+atropine vs.atropine,0.015 vs.0.11,RR 0.17,95%CI[0.06–0.49];penehyclidine+atropine vs.penehyclidine,0.13 vs.0.08,RR 0.23,95%CI[0.04–1.28]).Atropine combined with penehyclidine in OP patients also helped reduce the time to atropinization and AchE recovery,the rate of IMS and the rate of ADR.Compared with a single dose of atropine,a single dose of penehyclidine also signifi cantly elevated the cure rate,reduced times to atropinization,AchE recovery,and rate of IMS.CONCLUSION:Atropine combined with penehyclidine benefi ts OP patients by enhancing the cure rate,mortality rate,time to atropinization,AchE recovery,IMS rate,total ADR and duration of hospitalization.Penehyclidine combined with atropine is likely a better initial therapy for OP patients than atropine alone.
基金Project supported by the Outstanding Youth Fund of National Natural Science Foundation of China, the National Key Basic Research Support Foundation (NKBRSF) of China (No. 2002CB410805) and the Federal Ministry of Education and Research, Germany.
文摘Two procedures were compared for extraction and clean-up of 20organophosphorus and 19 pyrethroid pesticides in sediment to identify the more effective procedurefor groups of pesticides or individual compounds. In Procedure I, methanol/water and n-hexane wereused for extraction, and 1:10 (v/v) dichloromethane in n-hexane and acetone were used as eluents foreluting the analyte through the cartridge, with one evaporating steps on a rotary evaporator andtwo eluting steps on the cartridge. n-hexane/acetone (2:1, v/v) was used for extraction and elutionin Procedure II with one evaporating step on a rotary evaporator and one eluting step on thecartridge. All extractions were performed under an ultrasonic bath and gas chromatography and massspectrometry were utilized for measurements. Procedure II was developed as a rapid, timesaving, lesscostly and safer substitute for Procedure I which was an old method. Procedure II was moreeffective for almost all the organophosphorus pesticides tested and 11of the 19 pyrethroidpesticides, while Procedure I was more appropriate for analysis of 5 pyrethroid pesticides. However,recoveries of most pyrethroid pesticides were fairly low. Thus, further studies should focus onadjustment and formulation of solvents for more efficient extraction and clean-up of pyrethroidpesticides from sediment samples.
基金Supported by the Malek-Ashtar University of Technology(925826018,2015)
文摘The plant cellulose powder was activated by two different methods using 1,4-butanediol diglycidyl ether(BTDE)and 1,1′-Carbonyldiimidazole(CDI) as the chemical coupling agents.Organophosphorus hydrolase(OPH) from Flavobacterium ATCC 27551 was immobilized on any of activated support through covalent bonding.The optimal conditions of affecting parameters on enzyme immobilization in both methods were found, and it was demonstrated that the highest activity yields of immobilized OPH onto epoxy and CDI treated cellulose were 68.32%and 73.51%, respectively.The surface treatment of cellulose via covalent coupling with BTDE and CDI agents was proved by FTIR analysis.The kinetic constants of the free and immobilized enzymes were determined, and it was showed that both immobilization techniques moderately increased the Kmvalue of the free OPH.The improvements in storage and thermal stability were investigated and depicted that the half-life of immobilized OPH over the surface of epoxy modified cellulose had a better growth compared to the free and immobilized enzymes onto CDI treated support.Also, the pH stability of the immobilized preparations was enhanced relative to the free counterpart and revealed that all enzyme samples would have the same optimum pH value for stability at 9.0.Additionally, the immobilized OPH onto epoxy and CDI activated cellulose retained about 59% and 68% of their initial activity after ten turns of batch operation, respectively.The results demonstrated the high performance of OPH enzyme in immobilized state onto an inexpensive support with the potential of industrial applications.
基金Supported by the National Natural Science Foundation of China(41473070,31270544)Engineering Research Center Program of Tianjin(17PTGCCX00240)the National Water Pollution Control and Treatment Science and Technology Major Project(2015ZX07203–011-06)
文摘Organophosphorus pesticides(OPPs) are a set of toxic persistent organic pollutants(POPs) present in the environment. Recently, biochar-mediated bioremediation has exhibited many advantages over conventional methods for the remediation of pesticide-contaminated soil. In the present study, biochar and nitrogen fertilizer(NH_4NO_3)were employed to remediate OPP-contaminated soil and the greenhouse gas(GHG) emission during 90 days of incubation was investigated. After thermal desorption treatment, the content of organophosphorus pesticides reduced from 175.61 μg·kg^(-1) to 62.68 μg·kg^(-1). The addition of NH_4NO_3 in the following bioremediation led to larger reduction(34.35%) of the pesticide concentration than that of biochar(31.90%) for the contaminated soils with thermal desorption treatment, while the simultaneous addition of biochar and NH_4NO_3 led to the largest reduction of pesticide concentration(11.07%) for the soil without thermal desorption treatment. The addition of biochar and NH_4NO_3 only slightly increased the emission rate of GHGs from the soil without thermal treatment,but remarkably increased the emission rate of GHGs from the soil after thermal treatment. In most cases, the addition of NH_4NO_3 is more effective than biochar to promote the degradation of pesticide, but also exhibited higher GHG emission. The microbial community analysis suggests that the enhanced degradation of pesticide is mainly owing to the increased activity of microorganism.
基金Project supported by the National Basic Research Program (973) of China (No.2009CB119000)the National Natural Science Foundation of China (Nos.20707022,41073090,and 30771255)the Zhejiang Provincial Natural Science Foundation of China (No.Y507220)
文摘The widespread use of organophosphorus pesticides(OPs) poses a great threat to human health and has made the detection of OP residues in food an important task,especially in view of the fact that easy and rapid detection methods are needed.Because OPs have inhibitory effects on the activity of α-naphthyl acetate esterase(ANAE) in plants,in this work we evaluated the possibility of detecting OPs in vegetables with ANAE extracted from commercial flour.The limits of detection(LODs) obtained for methamidophos,dichlorvos,phoxim,dimethoate,and malathion in lettuce samples with crude ANAE were 0.17,0.11,0.11,0.96,and 1.70 mg/kg,respectively.Based on the maximum residue limits(MRLs) for OPs in food stipulated by Chinese laws which are 0.05,0.20,0.05,1.00,and 8.00 mg/kg for methamidophos,dichlorvos,phoxim,dimethoate,and malathion,respectively,the esterase inhibition method with crude ANAE had sufficient sensitivity to detect the residues of dichlorvos,dimethoate,and malathion in lettuce,but it could not be used to guarantee the safety of the same samples if methamidophos or phoxim residue was present.The sensitivity of the method was improved by the use of esterase purified by ammonium sulfate salting-out.The LODs obtained for methamidophos and phoxim with purified esterase were lower than the MRLs for these OPs in food.This is a very promising method for the detection of OP residues in vegetables using crude or purified esterase because of its cheapness,sensitivity,and convenience.
基金1Project supported by the Outstanding Youth Fund of the National Natural Science Foundation of China (No. 40325001),the National Key Basic Research Support Foundation of China (Nos. 2002CB415203 and 2002CB410805) and the Knowl-edge Innovation Program of
文摘The objectives of this study were to optimize instrumental parameters and conditions for analysis of selected organop- hosphorus pesticides (OPPs) by gas chromatography (GC) with nitrogen-phosphorus detection (NPD) (GC-NPD); to select an appropriate solvent system; to conduct a comparison of sonication and shaking extractions; and to select an appropriate procedure for extracting organophosphorus pesticides from soils. Procedure I consisted of n-hexane or petroleum ether together with acetone used as solvents, while Procedure contained several solvents including acetone, methanol, dichloromethane, and n-hexane or petroleum ether. Experimental results indicated that a mixture of petroleum ether/acetone (2:1, v/v) could be used in place of n-hexane/acetone (2:1, v/v) as it was a less expensive solvent system. In addition, shaking under a water bath at 20 °C was more effective than sonication. Also, Procedure I was more effective, safer, and more timesaving than Procedure Procedure I was applied to three soil types of different organic matter content, with recoveries of the OPPs from the yellow-brown soils, which had a higher organic matter content, being lower than those from the yellow and red soils.
文摘Pesticides have the potential to leave harmful effects on humans, animals, other living organisms, and the environment. Several human metabolic proteins inhibited after exposure to organophosphorus pesticides absorbed through the skin, inhalation, eyes and oral mucosa, are most important targets for this interaction study. The crystal structure of five different proteins, PDBIDs: 3LII, 3NXU, 4GTU, 2XJ1 and 1YXA in Homo sapiens (H. sapiens), interact with organophosphorus pesticides at the molecular level. The 3-D structures were found to be of good quality and validated through PROCHECK, ERRAT and ProSA servers. The results show that the binding energy is maximum -45.21 relative units of cytochrome P450 protein with phosmet pesticide. In terms of H-bonding, methyl parathion and parathion with acetylcholinesterase protein, parathion, methylparathion and phosmet with protein kinase C show the highest interaction. We conclude that these organophosphorus pesticides are more toxic and inhibit enzymatic activity by interrupting the metabolic pathways in H. sapiens.
基金湖南省科技厅重点研发计划(2017N K 2144)长沙市科技局重大专项(kq1804016)+1 种基金湖南农业科技创新联盟项目(2017LM0305)重金属污染耕地安全高效利用湖南省工程研究中心开放研究基金(TGOP-001)。
文摘In order to obtain high-efficiency organophosphorus solubilizing bacteria, 21 strains of organophosphate solubilizing bacteria were isolated from the rhizosphere soil of Camellia oleifera plants, and the transparent circle method was used for rescreening. Only 4 strains of bacteria could form transparent circle on organophosphorus medium. The D/d value of 4 strains of bacteria was between 1.62 and 2.71, among which the D/d value of strain Y6 was the highest(2.71). The available phosphorus content of the fermentation supernatant was 8.50~14.79 mg/L, which was 7.88~14.17 mg/L higher than that of CK. The strain Y6 had the highest soluble phosphorus content of 14.79 mg/L in the fermentation supernatant, which was 14.17 mg/L higher than that of CK. According to the colony morphology, physiological and biochemical characteristics and 16S rDNA sequence analysis of strain Y6, it is preliminarily determined that strain Y6 is Pseudomonas. Strain Y6 is beneficial to improve the supply of phosphorus in rhizosphere soil of Camellia oleifera and promote the growth of Camellia oleifera. It has great potential in the development of bio-organic fertilizer.
文摘[Objectives ] The paper was to explore enzyme inhibition rate method for rapid detection of organophosphorus and carbamate pesticides in cowpea. [ Methods ] Acetylcholinesterase (ACHE) was added to cowpea extract, to determine the inhibition rate of extract against enzyme. The influences of different sampiing methods and sampling parts on detection results were compared. [ Results] The positive rate of standard sampling was 18.18% higher than that of non-stand- ard sampling, and the positive rate of samples collected from cowpea tail was 16.67% higher than that collected from other parts. [ Condmions] Enzyme inhibi- tion rate method is suitable for rapid detection of organophosphorus and carbamate pesticides in cowpea.
基金Supported by Post-doctoral Scientific Fund of China(No.2017M611382)Autonomy Program of Economy,Trade and Information Commission of Shenzhen Municipality(No.20170427160059840)
文摘[ Objectives] This study was conducted to establish a QuEChERS-gas chromatography method for determination of eight kinds of organophosphorus pesticide residues in pepper. [Methods] The samples were extracted by acetonitrile, and anhydrous magnesium sulfate was used for salting out. The extracts were then purified by dispersive solid phase extraction combining with GCB, C18 and PSA. Samples were analyzed by FPD detector. External standard was used as quantitive method. [ Results] The detection limits were in the range of 0. 001 -0. 008 mg/kg, the average recoveries ranged from 83.5% to 101.2% , and the relative standard deviation (RSD) of the eight organophosphorus pesticide residues were below 5%. [ Conclusions] The method is simple, quick, easy and effective for the determination of pepper.
基金This work was supported by the grant from National 973 Project (2002CB512902) and the grant from Shanghai Shuguang Program.
文摘To examine a) the effect of organophosphorus pesticide exposure on activity of carboxylic esterases, namely butyrylcholinesterase (BChE), carboxylesterase (CarbE) and paraoxonase (PonE); and b) the association of polymorphisms of BChE and PonE with individual genetic susceptibility to organophosphorus pesticide exposure. Methods A cross-sectional study was conducted in 75 workers exposed to organophosphorus pesticides and 100 non-exposed controls. The serum activity of these enzymes was measured. Variant forms of BCHE-K, PON-192, and PON-55 were detected. A symptom score was developed as a proxy measure of clinical outcomes. Results Activities of both BChE and CarbE were lower in exposed workers (27.3±21.65 runol.hl.mL^-l and 235.6±104.03 nmol-min^-l.mL^-l) than in non-exposed workers (78.313±30.354 nmol.h^-l.mL^-1 and 362.681_+194.997 nmol.min^-1.mL^-1). The activity of PonE was not associated with exposure status. The AChE activity in the exposed workers with BCHE-K genotype UU (61 cases), genotype UK (12 cases) and genotype KK (2 cases) was 105.05, 84.42 and 79.00 mmol-h^-1.mL^-1, respectively and the accumulative symptom scores were 3.74, 9.17, and 12.50 accordingly. The AChE activity in the exposed workers with PON-192 genotype BB (37), genotype AB (27) and genotype AA (11) was 116.8, 91.2, and 72,3 mmol-h^-1.mL^-1, respectively and the symptom scores were 2.00, 6.74, and 9.73 accordingly. The AChE activity in those with PON-55 genotype LL (70) and genotype LM (5) was 102.4 and 82.8 mmol-h^-1.mL^-1 and the symptom scores were 4.53 and 9.20. The symptom score was the highest in individuals with abnormal homozygote for each of the three gene loci. Condusions Long-term exposure to organophosphorus pesticides can inhibit BChE and CarbE activity, but exerts no inhibitory effect on PonE activity. Different genotypes of BCHE-K, PON-192, and PON-55 may be related to the severity of adverse health effects of organophosphorus pesticide exposure. Implications of potentially higher susceptibility of workers with mutant homozygotes should be evaluated to reduce health risks.
基金Project supported by the National Key Technology R&D Program of China(No.2007BAD59B06)the International Science and Technology Cooperation Program of China(No.2007DFA31260)
文摘We constructed an expression cassette of the organophosphorus pesticide degrading(opal)gene under the control of the E8 promoter.Then opd was transformed into tomato fruit using an agroinfiltration transient expression system.β-Glucuronidase(GUS)staining,reverse transcription-polymerase chain reaction(RT-PCR),wavelength scanning,and fluorescent reaction were performed to examine the expression of the opd gene and the hydrolysis activity on coumaphos of organo-phosphorus hydrolase(OPH)in tomato fruit.The results show that the agroinfiltrated tomato fruit-expressed OPH had the maximum hydrolysis activity of about 11.59 Uhng total soluble protein.These results will allow us to focus on breeding transgenic plants that could not only enhance the degrading capability of fruit and but also hold no negative effects on pest control when spraying organophosphorus pesticides onto the seedlings in fields.