In recent years,neonicotinoids(NEOs)and organophosphate esters(OPEs)have been widely used as substitutes for traditional pesticides and brominated fame-retardants,respectively.Previous studies have shown that those co...In recent years,neonicotinoids(NEOs)and organophosphate esters(OPEs)have been widely used as substitutes for traditional pesticides and brominated fame-retardants,respectively.Previous studies have shown that those compounds can be frequently detected in environmental and human samples,are able to penetrate the placental barrier,and are toxic to animals.Thus,it is reasonable to speculate that NEOs and OPEs may have potential adverse effects in humans,especially during development.We employed a human embryonic stem cell differentiation-and liver S9 fraction metabolism-based fast screening model to assess the potential embryonic toxicity of those two types of chemicals.We show that four NEO and five OPE prototypes targeted mostly ectoderm specification,as neural ectoderm and neural crest genes were down-regulated,and surface ectoderm and placode markers up-regulated.Human liver S9 fraction's treatment could generally reduce the effects of the chemicals,except in a few specific instances,indicating the liver may detoxify NEOs and OPEs.Our findings suggest that NEOs and OPEs interfere with human early embryonic development.展开更多
The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system...The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system using manganese catalyst(Mn NC)and cobalt catalyst(Co NC)to trigger the nonradical oxidation and synergistic oxidation pathway,respectively to remove NEOs.The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability.The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes.The charge distribution and reaction sites of various NEOs were analyzed using density functional theory(DFT)calculations,and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents.Nitro group(–NO_(2))and cyanide group(–C≡N)were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals.The transformation of NEOs was analyzed,and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks.S and N atoms,which possess strong electronegativity and high electron cloud density,were identified as key active sites in the degradation pathway.The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.展开更多
Water-bridged H-bonds have been observed in many cases of ligand-receptor recognitions. To explore the roles of water bridges in the binding of neonicotinoids with receptors, twenty-four neonicotinoid compounds with n...Water-bridged H-bonds have been observed in many cases of ligand-receptor recognitions. To explore the roles of water bridges in the binding of neonicotinoids with receptors, twenty-four neonicotinoid compounds with nine fragments, including 1 H-1,2,3-triazole, CN, COOMe, CONHNH_2, CONHMe, NO_2,NH_2, NHCOMe and NHCSNH_2 were synthesized and evaluated, of which, compounds with cyano group showed the best activities against Aphis craccivora. Accordingly, the cyano group is the optimal fragment mimicking the water bridge. Two cyano-substituted cis-nitromethylene compounds display good insecticidal activities, whereas the LC_(50) values are lower than those of their corresponding prototypes.Docking study showed that the cyano group acts only as H-bond acceptor, while the water bridge can act as both donor and acceptor. It revealed that the water bridge might be stable in the active site and was not suitable to be replaced by other groups. The findings illustrated that the water bridge is necessary for high insecticidal activities of neonicotinoids, which should be also helpful in better understanding the binding mode of neonicotinoids.展开更多
Twenty-four novel neonicotinoid analogues with nitromethylene and five-membered aromatic heterocycles were designed and synthesized.All target molecular structures have been confirmed by analytical and spectral data.S...Twenty-four novel neonicotinoid analogues with nitromethylene and five-membered aromatic heterocycles were designed and synthesized.All target molecular structures have been confirmed by analytical and spectral data.Some compounds exhibited notable insecticidal activities against aphid(Aphis medicaginis)and brown planthopper(Nilaparvata lugens).The aqueous stability test confirmed that the stabilities of those compounds were superior to the leading compound,and the photostability was even better than that of imidacloprid.展开更多
This study was mainly made on the role of energy revisers in cotton aphid, Aphis gossypii Glover （Hemiptera： Aphididae） countered with imidacloprid and thiametoxam. We measured used energy, available energy and the...This study was mainly made on the role of energy revisers in cotton aphid, Aphis gossypii Glover （Hemiptera： Aphididae） countered with imidacloprid and thiametoxam. We measured used energy, available energy and the content of total energy in three strains of cotton aphid which were from very resistant to neonicotinoid, sup to semi-sensitive and sensitive speccies, respectively. It was observed changes in energy resources rate in all of the aphid strains at which each substrate was metabolized under stress. Our findings indicated among energy sources, total lipid in susceptible strain was increased in counter of spraying and it was decreased in resistance and semi sensitive strains. Whereas, total protein was decreased in all of the strains encountering with neonicotiniod stress. Total glycogen was increased significantly in different aphid strains and sugar was decreased in countered of spraying.展开更多
Three populations of Aphis gossypii of distinct susceptibility to neonicotinoids show differences in the accumulation and mobilization of energy reserves,what may allow the production of their defensive tools against ...Three populations of Aphis gossypii of distinct susceptibility to neonicotinoids show differences in the accumulation and mobilization of energy reserves,what may allow the production of their defensive tools against two neonicotinoid insecticides without impairing their reproductive performance.Bioassays were also carried out for these aphid populations.According to the results obtained,the Ag-R population showed resistant rate significantly higher than the other two populations.Levels of some biochemical characteristics were determined in the resistant,susceptible and semi susceptible populations of cotton aphid.The results obtained in the assays with biochemical parameters indicated significant differences in activity among the populations,with higher activity in using glycogen in the Ag-R population.The inverse activity trends oft(generation time)and DT(doubling time)in both resistant and susceptible populations,one showing fitness disadvantage without insecticide exposure and the other not showing it,may underlay the mitigation of insecticide resistance physiological costs observed in the Ag-R population.展开更多
A series of novel bridged-neonicotinoid analogues were designed and synthesized, which were constructed by starting material 8 with cyclopentenone or cyclohexenone in the presence of catalyst aluminium chloride. All o...A series of novel bridged-neonicotinoid analogues were designed and synthesized, which were constructed by starting material 8 with cyclopentenone or cyclohexenone in the presence of catalyst aluminium chloride. All of the compounds were characterized and confirmed by^1H NMR,^（13）C NMR, HRMS and IR. The bioassay tests showed that compounds 5 and 6a showed higher bioactivities than imidacloprid against Aphis craccivora.展开更多
The global insecticide market is undergoing significant changes,witnessing a surge in neonicotinoids(NEOs)usage,alongside the persistent application of traditional insecticides,such as organophosphates(OPs),carbamates...The global insecticide market is undergoing significant changes,witnessing a surge in neonicotinoids(NEOs)usage,alongside the persistent application of traditional insecticides,such as organophosphates(OPs),carbamates(CMs)and pyrethroids(PYRs).In this study,therefore,NEOs,OPs,PYRs and CMs were measured in various pomelo tissues and paired soil and leaf samples collected from two pomelo orchards in South China.NEOs exhibited a higher median sum residue in pulp(∑NEOs:1.90 ng/g)than traditional insecticides(∑OPs:1.69 ng/g,∑CMs:0.49 ng/g,and ∑PYRs:0.33 ng/g).Principal component analysis indicated that NEO residues in pulp was primarily originated from deep soil.Moreover,the migration pathway of NEOs potentially extends from the deep soil to the plant's root system,then travels through the carpopodium to access the pulp,whereas traditional insecticides adhere to a migration pathway that progresses from the epicarp to the pulp.Tissue-specific distribution analysis revealed that NEOs exhibit an enhanced propensity for accumulation in the pulp.In contrast,traditional insecticides display a preference for accumulating in seeds and endocarp.This study first to delineate distinction in residue,migration,tissue-specific distribution between NEOs and traditional insecticides,heightened emphasis is warranted on NEOs and their metabolites within the ambit of the“One-Health”framework.展开更多
Molecular aggregation state of bioactive compounds plays a key role in bio-interactive procedure.Diverse ag-gregation states of bioactive compounds contribute to different biological or chemical properties.Water-bridg...Molecular aggregation state of bioactive compounds plays a key role in bio-interactive procedure.Diverse ag-gregation states of bioactive compounds contribute to different biological or chemical properties.Water-bridge,as the simple hetero-molecular aggregation,has been found bridging the binding between many bioactive compounds and their targets through hydrogen bonding network,e.g.in the recognition of neonicotinoids with insect nAChRs.To better understanding the roles of water-bridge on bioactivities of compounds,an approach of hetero-dimeric ag-gregation with water was proposed.Quantitative structure-activity relationship(QSAR)and pharmacophore mod-eling investigations were applied on 19 neonicotinoids,as well as their aggregates with water.The aggregate-based CoMSIA,PHASE and linear QSAR models presented better statistical significance and predictabilities than the monomer ones,which indicated that the bioactivities correlated with the aggregate properties and water bridged hy-drogen bond of the active site.All results revealed the essential roles of water-bridge in ligand recognition,which should be considered in future ligand design and optimization.展开更多
Background The real-world exposure levels of non-therapeutic antibiotics and neonicotinoids in type 1 diabetes(T1D)children and their associations as environmental triggers through gut microbiota shifts remained unkno...Background The real-world exposure levels of non-therapeutic antibiotics and neonicotinoids in type 1 diabetes(T1D)children and their associations as environmental triggers through gut microbiota shifts remained unknown.We thus investigated the antibiotics and neonicotinoids’exposure levels and their associations with gut microbiota in pediatric T1D.Methods Fifty-one newly onset T1D children along with 67 age-matched healthy controls were recruited.Urine concentrations of 28 antibiotics and 12 neonicotinoids were measured by mass spectrometry.Children were grouped according to the kinds of antibiotics’and neonicotinoids’exposures,respectively.The 16S rRNA of fecal gut microbiota was sequenced,and the correlation with urine antibiotics and neonicotinoids’concentrations was analyzed.Results The overall detection rates of antibiotics were 72.5%and 61.2%among T1D and healthy children,whereas the neonicotinoids detection rates were 70.6%and 52.2%(P=0.044).Children exposed to one kind of antibiotic or two or more kinds of neonicotinoids had higher risk of T1D,with the odd ratios of 2.579 and 3.911.Furthermore,co-exposure to antibiotics and neonicotinoids was associated with T1D,with the odd ratio of 4.924.Antibiotics or neonicotinoids exposure did not affect overall richness and diversity of gut microbiota.However,children who were exposed to neither antibiotics nor neonicotinoids had higher abundance of Lachnospiraceae than children who were exposed to antibiotics and neonicotinoids alone or together.Conclusion High antibiotics and neonicotinoids exposures were found in T1D children,and they were associated with changes in gut microbiota featured with lower abundance of butyrate-producing genera,which might increase the risk of T1D.展开更多
Imidacloprid,a neonicotinoid insecticide,is widelyused in agriculture as a safer alternative to highly toxicorganophosphates.It targets nicotinic acetylcholinereceptors in pests and is generally low in toxicity tohuma...Imidacloprid,a neonicotinoid insecticide,is widelyused in agriculture as a safer alternative to highly toxicorganophosphates.It targets nicotinic acetylcholinereceptors in pests and is generally low in toxicity tohumans.However,large ingestions can cause severe,life-threatening complications,with no establishedtreatment protocols.Though rarely fatal,imidaclopridpoisoning is increasingly reported in agricultural regions,particularly in Southeast Asia,with most cases involvingsuicide attempts.展开更多
Neonicotinoid insecticides(NEOs)have become an integral part of the global insecticide market due to their high efficiency and low toxicity.However,their environmental persistence has raised significant ecological con...Neonicotinoid insecticides(NEOs)have become an integral part of the global insecticide market due to their high efficiency and low toxicity.However,their environmental persistence has raised significant ecological concerns.Dongting Lake represents a vital freshwater lake in China,and its ecosystem health directly affects regional ecological balance and people’s livelihoods.This study systematically investigated the occurrence characteristics and ecological risks of NEOs in water bodies and sediments across the Dongting Lake basin.Based on surface water and sediment samples collected from 26 representative sampling sites,this study quantified nine NEOs using liquid chromatography triple quadrupole mass spectrometry.Furthermore,it assessed ecological risks posed by the NEOs using the risk quotient(RQ)method and fugacity modeling.The results revealed the presence of six NEOs in the water bodies:imidacloprid(IMI),acetamiprid(ACE),clothianidin(CLO),thiamethoxam(THIA),flonicamid(FLO),and dinotefuran(DIN).The total concentrations of these six NEOs averaged 275.11 ng/L.Five predominant NEOs(i.e.,IMI,THIA,ACE,CLO,and DIN)were identified in the sediments,with a mean concentration of 0.31 ng/g.The NEO concentrations in the water bodies across the Dongting Lake basin increased in the order of the Xiangjiang,Zishui,Yuanjiang,and Lishui rivers(collectively referred to as the Four Rivers),the mainstream of Dongting Lake,the Xinqiang River,the Miluo River,and the Hudu,Ouchi,and Songzi rivers(collectively referred to as the Three Outlets).Sediments from tributaries progressively accumulate in the lake.The ecological risk assessment identified IMI and DIN as the highest-risk compounds(RQ>1),with high-risk areas concentrated in the mainstream of Dongting Lake and the Ouchi,Miluo,and Hudu rivers.The fugacity model showed that IMI,ACE,and THIA are prone to diffuse from sediments to water bodies in most areas,with fugacity fractions(ff)values of greater than 0.5.In contrast,the mainstream of Dongting Lake acts as a sink of CLO and DIN(ff values:<0.5).Sediments at the lake’s outlet emerge as an important sink of NEOs.Based on the results of this study,it is advisable to strengthen the supervision of NEO applications in agricultural areas and to implement zonal control strategies.These measures will help reduce ecological risks and protect the safety of water ecosystems in the Dongting Lake region.展开更多
The extensive use of neonicotinoids on food crops for pest management has resulted in substantial environmental contamination.It is imperative to develop an effective remediation material and technique as well as to d...The extensive use of neonicotinoids on food crops for pest management has resulted in substantial environmental contamination.It is imperative to develop an effective remediation material and technique as well as to determine the evolution pathways of products.Here,novel ball-milled nitrogen-doped biochar(NBC)-modified zero-valent iron(ZVI)composites(named MNBC-ZVI)were fabricated and applied to degrading neonicotinoids.Based on the characterization results,NBC incorporation introduced N-doped sites and new allying heterojunctions and achieved surface charge redistribution,rapid electron transfer,and higher hydrophobicity of ZVI particles.As a result,the interaction between ZVI particles and thiamethoxam(a typical neonicotinoid)was improved,and the adsorption-desorption and reductive degradation of thiamethoxam and·H generation steps were optimized.MNBC-ZVI could rapidly degrade 100%of 10 mg·L^(−1) thiamethoxam within 360 min,its reduction rate constant was 12.1-fold greater than that of pristine ZVI,and the electron efficiency increased from 29.7%to 57.8%.This improved reactivity and selectivity resulted from increased electron transfer,enhanced hydrophobicity,and reduced accumulation of iron mud.Moreover,the degradation of neonicotinoids occurred mainly via nitrate reduction and dichlorination,and toxicity tests with degradation intermediates revealed that neonicotinoids undergo rapid detoxification.Remarkably,MNBCZVI also presented favorable tolerance to various anions,humic acid,wastewater and contaminated soil,as well as high reusability.This work offers an efficient and economic biochar-ZVI remediation technology for the rapid degradation and detoxification of neonicotinoids,significantly contributes to knowledge on the relevant removal mechanism and further advances the synthesis of highly reactive and environmentally friendly materials.展开更多
Thiacloprid has been banned in many European countries for its toxicity, but is nevertheless still used outside the EU. Using the ant Myrmica sabuleti as a model organism, we sought a concentration of thiacloprid that...Thiacloprid has been banned in many European countries for its toxicity, but is nevertheless still used outside the EU. Using the ant Myrmica sabuleti as a model organism, we sought a concentration of thiacloprid that would be low in environmental impact, but nonetheless harmful to an insect. Assessed on ten biological traits, a sub-lethal 2 μg/L concentration in the sugar water diet of the ants impacted their locomotion and other motor-linked behavioral traits such as orientation, moving on an unfamiliar device, moving on a rough surface, brood caring and progressing along a twist and turns path. Sensory perception appeared unaffected. Behaviors involving cognition or related in some way to it, such as social relationships, ability to leave an enclosure, learning and memory also appeared unaffected, but their outcomes could be entangled with those of locomotor impairment. The effect of thiacloprid on locomotion vanished in about 30 hours. Adverse effects were still present with the 0.1 and 0.01 μg/L concentrations, but at a lower level. Partial physiological adaptation at the individual level occurred for the 2 μg/L concentration, less so for 0.1 μg/L and not for 0.01 μg/L. Thiacloprid should thus be used at the lowest still active concentration producing a significant damaging behavioral effect with no physiological adaptation. This concentration remains to be specifically defined for targeted pest species.展开更多
Four strains of the Q biotype and one of the B biotype of the whitefly Bemisia tabaci collected from China were characterised for resistance to four neonicotinoid insecticides and pymetrozine.Q biotype strains showed ...Four strains of the Q biotype and one of the B biotype of the whitefly Bemisia tabaci collected from China were characterised for resistance to four neonicotinoid insecticides and pymetrozine.Q biotype strains showed moderate to strong resistance to imidacloprid,thiamethoxam and acetamiprid,but little or no cross-resistance to dinotefuron.Resistance to neonicotinoids was consistently associated with resistance to pymetrozine,despite the latter having a distinct（though unresolved）mode of action.The single B biotype strain proved largely susceptible to all the insecticides investigated.Resistance in the Q biotype strains was associated with over-expression of a cytochrome P450 monooxygenase gene,CYP6CM1,whose substrate specificity presumably accounts for the observed cross-resistance profiles.展开更多
Pyrethroids,organophosphorus pesticides and fipronil have been listed as priority chemicals in human biomonitoring studies because of their wide use and potential health effects in humans.The determination of 13 pesti...Pyrethroids,organophosphorus pesticides and fipronil have been listed as priority chemicals in human biomonitoring studies because of their wide use and potential health effects in humans.The determination of 13 pesticides,including pyrethroids(deltamethrin,cypermethrin,permethrin,cyfluthrin,bifenthrin),organophosphorus(chlorpyrifos,chlorpyrifosmethyl,and malathion),fipronil,neonicotinoids(imidacloprid,acetamiprid and thiacloprid)and triazole(prothioconazole),together with 13 corresponding metabolites in human urine samples was achieved by solid-phase extraction and analysis by liquid chromatography coupled to tandem mass spectrometry.All targeted compounds,except malathion dicarboxylic acid,were measured with a mean within-accuracy(n=5)of 71%–114%(RSD:1%–14%)and between-run(n=15)accuracy of 80%–118%(RSD:2%–14%).Limits of quantitation of the targeted analytes ranged from 0.1 to 16 pg/m L.The detection result of urine samples from 25 volunteers indicated that the detection frequencies of 3,5,6-trichloro-2-pyridinol(median:448 pg/m L),6-chloropyridine-3-carboxylic acid(median:193 pg/m L),2-methyl-3-phenylbenzoic acid(median:181 pg/m L),3-phenoxybenzoic acid(median:99 pg/m L),2-isopropyl-6-methyl-4-pyrimidinol(median:77 pg/m L),cyfluthrin(median:59 pg/m L),cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid(cis-DCCA,median:53 pg/m L),trans-DCCA(median:25 pg/m L),prothioconazole(median:21 pg/m L),imidacloprid(median:7 pg/m L),and prothioconazole-desthio(median:1 pg/m L)were>50%.The obtained results show that the validated method is suitable for the human biomonitoring of these currentuse pesticides and their metabolites.展开更多
A series of new hexahydroimidazo[1,2-a]pyridine derivatives were synthesized via convenient and practical three-component reactions. Preliminary bioassays showed that majority of the target compounds exhibited moderat...A series of new hexahydroimidazo[1,2-a]pyridine derivatives were synthesized via convenient and practical three-component reactions. Preliminary bioassays showed that majority of the target compounds exhibited moderate to excellent insecticidal activity against cowpea aphids （Aphis craccivora）. Among them, compound 91 demonstrated significant activity with LCso value of 0.00918 mmol/L which was about 3.8-fold higher than that of imidacloprid （IMI）. Furthermore, the study of stereostructure-activity relationship of four isomers of 9k indicated that configuration played a key role in insecticidal activity of these compounds.展开更多
A series of novel neonicotinoids derivatives 4a―4p was designed and synthesized by introducing the ethylbenzene group into the thiazole ring, their structures were confirmed by IR, 1H NMR and elemental analysis. The ...A series of novel neonicotinoids derivatives 4a―4p was designed and synthesized by introducing the ethylbenzene group into the thiazole ring, their structures were confirmed by IR, 1H NMR and elemental analysis. The crystal structure of compound 4j has been determined by X-ray diffraction analysis.展开更多
A series of novel tetrahydroimidazo[1,2-a]pyridine-5（1H）-one derivatives containing a electronegative pharmacophore（=CNO_2） were synthesized via practical aza-ene reaction and characterized by ~1H NMR,^（13）C NM...A series of novel tetrahydroimidazo[1,2-a]pyridine-5（1H）-one derivatives containing a electronegative pharmacophore（=CNO_2） were synthesized via practical aza-ene reaction and characterized by ~1H NMR,^（13）C NMR,^（19）F NMR and HRMS. Preliminary bioassays showed that some of the target compounds exhibited good insecticidal activity against brown planthopper（Nilaparvata lugens） and cowpea aphids（Aphis craccivora） at 500 mg L^（-1）. Among them, compound 11 h was active against brown planthopper at100 mg L^（-1）. The insecticidal activities varied significantly depending on the types and patterns of the substituents, which provided guidance for further investigation on structure modifications.展开更多
Alzheimer’s disease(AD)is a progressive and neurodegenerative illness which results in alterations in cognitive development.It is characterized by loss/dysfunction of cholinergic neurons,and formation of amyloid plaq...Alzheimer’s disease(AD)is a progressive and neurodegenerative illness which results in alterations in cognitive development.It is characterized by loss/dysfunction of cholinergic neurons,and formation of amyloid plaques,and formation of neurofibrillary tangles,among other changes,due to hyperphosphorylation of tau-protein.Exposure to pesticides in humans occurs frequently due to contact with contaminated food,water,or particles.Organochlorines,organophosphates,carbamates,pyrethroids and neonicotinoids are associated with the most diagnosed incidents of severe cognitive impairment.The aim of this study was to determine the effects of these pesticides on the phosphorylation of tau protein,and its cognitive implications in the development of AD.It was found that exposure to pesticides increased the phosphorylation of tau protein at sites Ser198,Ser199,Ser202,Thr205,Ser396 and Ser404.Contact with these chemicals altered the enzymatic activities of cyclin-dependent kinase 5 and glycogen synthase kinase 3 beta,and protein phosphatase-2A.Moreover,it altered the expression of the microtubule associated protein tau gene,and changed levels of intracellular calcium.These changes affected tau protein phosphorylation and neuroinflammation,and also increased oxidative stress.In addition,the exposed subjects had poor level of performance in tests that involved evaluation of novelty,as test on verbal,non-verbal,spatial memory,attention,and problem-solving skills.展开更多
基金supported by the Ministry of Science and Technology of the People’s Republic of China (No.2020YFA0907500)the National Natural Science Foundation of China (Nos.22150710514,22021003,and 22106174)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDPB200202)the Postdoc Science Foundation of China (No.2021M693322)。
文摘In recent years,neonicotinoids(NEOs)and organophosphate esters(OPEs)have been widely used as substitutes for traditional pesticides and brominated fame-retardants,respectively.Previous studies have shown that those compounds can be frequently detected in environmental and human samples,are able to penetrate the placental barrier,and are toxic to animals.Thus,it is reasonable to speculate that NEOs and OPEs may have potential adverse effects in humans,especially during development.We employed a human embryonic stem cell differentiation-and liver S9 fraction metabolism-based fast screening model to assess the potential embryonic toxicity of those two types of chemicals.We show that four NEO and five OPE prototypes targeted mostly ectoderm specification,as neural ectoderm and neural crest genes were down-regulated,and surface ectoderm and placode markers up-regulated.Human liver S9 fraction's treatment could generally reduce the effects of the chemicals,except in a few specific instances,indicating the liver may detoxify NEOs and OPEs.Our findings suggest that NEOs and OPEs interfere with human early embryonic development.
基金funded by National Natural Science Foundation of China(No.42177382)。
文摘The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system using manganese catalyst(Mn NC)and cobalt catalyst(Co NC)to trigger the nonradical oxidation and synergistic oxidation pathway,respectively to remove NEOs.The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability.The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes.The charge distribution and reaction sites of various NEOs were analyzed using density functional theory(DFT)calculations,and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents.Nitro group(–NO_(2))and cyanide group(–C≡N)were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals.The transformation of NEOs was analyzed,and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks.S and N atoms,which possess strong electronegativity and high electron cloud density,were identified as key active sites in the degradation pathway.The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.
基金the financial supports from the National Natural Science Foundation of China (Nos. 21572059, 21172070)Innovation Program of Shanghai Municipal Education Commission (No. 201701070002E00037)
文摘Water-bridged H-bonds have been observed in many cases of ligand-receptor recognitions. To explore the roles of water bridges in the binding of neonicotinoids with receptors, twenty-four neonicotinoid compounds with nine fragments, including 1 H-1,2,3-triazole, CN, COOMe, CONHNH_2, CONHMe, NO_2,NH_2, NHCOMe and NHCSNH_2 were synthesized and evaluated, of which, compounds with cyano group showed the best activities against Aphis craccivora. Accordingly, the cyano group is the optimal fragment mimicking the water bridge. Two cyano-substituted cis-nitromethylene compounds display good insecticidal activities, whereas the LC_(50) values are lower than those of their corresponding prototypes.Docking study showed that the cyano group acts only as H-bond acceptor, while the water bridge can act as both donor and acceptor. It revealed that the water bridge might be stable in the active site and was not suitable to be replaced by other groups. The findings illustrated that the water bridge is necessary for high insecticidal activities of neonicotinoids, which should be also helpful in better understanding the binding mode of neonicotinoids.
基金supported by the Innovation Program of Shanghai Municipal Education Commission(No.201701070002E00037)the National Key Research Program of China(No.2017YFD0200505)。
文摘Twenty-four novel neonicotinoid analogues with nitromethylene and five-membered aromatic heterocycles were designed and synthesized.All target molecular structures have been confirmed by analytical and spectral data.Some compounds exhibited notable insecticidal activities against aphid(Aphis medicaginis)and brown planthopper(Nilaparvata lugens).The aqueous stability test confirmed that the stabilities of those compounds were superior to the leading compound,and the photostability was even better than that of imidacloprid.
文摘This study was mainly made on the role of energy revisers in cotton aphid, Aphis gossypii Glover （Hemiptera： Aphididae） countered with imidacloprid and thiametoxam. We measured used energy, available energy and the content of total energy in three strains of cotton aphid which were from very resistant to neonicotinoid, sup to semi-sensitive and sensitive speccies, respectively. It was observed changes in energy resources rate in all of the aphid strains at which each substrate was metabolized under stress. Our findings indicated among energy sources, total lipid in susceptible strain was increased in counter of spraying and it was decreased in resistance and semi sensitive strains. Whereas, total protein was decreased in all of the strains encountering with neonicotiniod stress. Total glycogen was increased significantly in different aphid strains and sugar was decreased in countered of spraying.
文摘Three populations of Aphis gossypii of distinct susceptibility to neonicotinoids show differences in the accumulation and mobilization of energy reserves,what may allow the production of their defensive tools against two neonicotinoid insecticides without impairing their reproductive performance.Bioassays were also carried out for these aphid populations.According to the results obtained,the Ag-R population showed resistant rate significantly higher than the other two populations.Levels of some biochemical characteristics were determined in the resistant,susceptible and semi susceptible populations of cotton aphid.The results obtained in the assays with biochemical parameters indicated significant differences in activity among the populations,with higher activity in using glycogen in the Ag-R population.The inverse activity trends oft(generation time)and DT(doubling time)in both resistant and susceptible populations,one showing fitness disadvantage without insecticide exposure and the other not showing it,may underlay the mitigation of insecticide resistance physiological costs observed in the Ag-R population.
基金financial supported by Shandong Provincial Natural Science Foundation (No. ZR2015BL009)The Key Research and Development Program of Shandong Provincial (No. 2016GGX107006)+1 种基金National Natural Science Foundation of China (No. 21501066)the Opening Project of Shanghai Key Laboratory of Chemical Biology
文摘A series of novel bridged-neonicotinoid analogues were designed and synthesized, which were constructed by starting material 8 with cyclopentenone or cyclohexenone in the presence of catalyst aluminium chloride. All of the compounds were characterized and confirmed by^1H NMR,^（13）C NMR, HRMS and IR. The bioassay tests showed that compounds 5 and 6a showed higher bioactivities than imidacloprid against Aphis craccivora.
基金The Natural Science Foundation of China(No.22022612,No.22036004,No.22306209,and No.42307369)Natural Science Foundation of Guangdong Province,China(No.2020A0104006 and No.2021A1515010243)+1 种基金China Postdoctoral Science Foundation(No.2022M723587 and No.2023T160747)Department of Education of Guangdong Province(No.2021KQNCX087)are acknowledged for their partial research support.
文摘The global insecticide market is undergoing significant changes,witnessing a surge in neonicotinoids(NEOs)usage,alongside the persistent application of traditional insecticides,such as organophosphates(OPs),carbamates(CMs)and pyrethroids(PYRs).In this study,therefore,NEOs,OPs,PYRs and CMs were measured in various pomelo tissues and paired soil and leaf samples collected from two pomelo orchards in South China.NEOs exhibited a higher median sum residue in pulp(∑NEOs:1.90 ng/g)than traditional insecticides(∑OPs:1.69 ng/g,∑CMs:0.49 ng/g,and ∑PYRs:0.33 ng/g).Principal component analysis indicated that NEO residues in pulp was primarily originated from deep soil.Moreover,the migration pathway of NEOs potentially extends from the deep soil to the plant's root system,then travels through the carpopodium to access the pulp,whereas traditional insecticides adhere to a migration pathway that progresses from the epicarp to the pulp.Tissue-specific distribution analysis revealed that NEOs exhibit an enhanced propensity for accumulation in the pulp.In contrast,traditional insecticides display a preference for accumulating in seeds and endocarp.This study first to delineate distinction in residue,migration,tissue-specific distribution between NEOs and traditional insecticides,heightened emphasis is warranted on NEOs and their metabolites within the ambit of the“One-Health”framework.
基金We thanks for the financial supports from the Na-tional Natural Science Foundation of China(No.21172070)the National Key Technology R&D Pro-gram of China(No.2011BAE06B05)+2 种基金the National High Technology Research Development Program of China(No.2011AA10A207)the National Basic Re-search Program of China(No.2010CB126100)the Fundamental Research Funds for the Central Universi-ties(No.222201314006).
文摘Molecular aggregation state of bioactive compounds plays a key role in bio-interactive procedure.Diverse ag-gregation states of bioactive compounds contribute to different biological or chemical properties.Water-bridge,as the simple hetero-molecular aggregation,has been found bridging the binding between many bioactive compounds and their targets through hydrogen bonding network,e.g.in the recognition of neonicotinoids with insect nAChRs.To better understanding the roles of water-bridge on bioactivities of compounds,an approach of hetero-dimeric ag-gregation with water was proposed.Quantitative structure-activity relationship(QSAR)and pharmacophore mod-eling investigations were applied on 19 neonicotinoids,as well as their aggregates with water.The aggregate-based CoMSIA,PHASE and linear QSAR models presented better statistical significance and predictabilities than the monomer ones,which indicated that the bioactivities correlated with the aggregate properties and water bridged hy-drogen bond of the active site.All results revealed the essential roles of water-bridge in ligand recognition,which should be considered in future ligand design and optimization.
基金supported by the National Key Research and Development Program of China(2016YFC1305302)the Clinical special project of integrated traditional Chinese and Western medicine in 2019,Shanghai Municipal Health Commission,Shanghai Municipal Administrator of Traditional Chinese Medicine.
文摘Background The real-world exposure levels of non-therapeutic antibiotics and neonicotinoids in type 1 diabetes(T1D)children and their associations as environmental triggers through gut microbiota shifts remained unknown.We thus investigated the antibiotics and neonicotinoids’exposure levels and their associations with gut microbiota in pediatric T1D.Methods Fifty-one newly onset T1D children along with 67 age-matched healthy controls were recruited.Urine concentrations of 28 antibiotics and 12 neonicotinoids were measured by mass spectrometry.Children were grouped according to the kinds of antibiotics’and neonicotinoids’exposures,respectively.The 16S rRNA of fecal gut microbiota was sequenced,and the correlation with urine antibiotics and neonicotinoids’concentrations was analyzed.Results The overall detection rates of antibiotics were 72.5%and 61.2%among T1D and healthy children,whereas the neonicotinoids detection rates were 70.6%and 52.2%(P=0.044).Children exposed to one kind of antibiotic or two or more kinds of neonicotinoids had higher risk of T1D,with the odd ratios of 2.579 and 3.911.Furthermore,co-exposure to antibiotics and neonicotinoids was associated with T1D,with the odd ratio of 4.924.Antibiotics or neonicotinoids exposure did not affect overall richness and diversity of gut microbiota.However,children who were exposed to neither antibiotics nor neonicotinoids had higher abundance of Lachnospiraceae than children who were exposed to antibiotics and neonicotinoids alone or together.Conclusion High antibiotics and neonicotinoids exposures were found in T1D children,and they were associated with changes in gut microbiota featured with lower abundance of butyrate-producing genera,which might increase the risk of T1D.
文摘Imidacloprid,a neonicotinoid insecticide,is widelyused in agriculture as a safer alternative to highly toxicorganophosphates.It targets nicotinic acetylcholinereceptors in pests and is generally low in toxicity tohumans.However,large ingestions can cause severe,life-threatening complications,with no establishedtreatment protocols.Though rarely fatal,imidaclopridpoisoning is increasingly reported in agricultural regions,particularly in Southeast Asia,with most cases involvingsuicide attempts.
基金jointly supported by project of the China Geological Survey(DD20243375,DD20230478)the Key Research and Development Program of Hunan Province(2023SK2066)the Natural Science Foundation of Hunan Province(2024JJ7620).
文摘Neonicotinoid insecticides(NEOs)have become an integral part of the global insecticide market due to their high efficiency and low toxicity.However,their environmental persistence has raised significant ecological concerns.Dongting Lake represents a vital freshwater lake in China,and its ecosystem health directly affects regional ecological balance and people’s livelihoods.This study systematically investigated the occurrence characteristics and ecological risks of NEOs in water bodies and sediments across the Dongting Lake basin.Based on surface water and sediment samples collected from 26 representative sampling sites,this study quantified nine NEOs using liquid chromatography triple quadrupole mass spectrometry.Furthermore,it assessed ecological risks posed by the NEOs using the risk quotient(RQ)method and fugacity modeling.The results revealed the presence of six NEOs in the water bodies:imidacloprid(IMI),acetamiprid(ACE),clothianidin(CLO),thiamethoxam(THIA),flonicamid(FLO),and dinotefuran(DIN).The total concentrations of these six NEOs averaged 275.11 ng/L.Five predominant NEOs(i.e.,IMI,THIA,ACE,CLO,and DIN)were identified in the sediments,with a mean concentration of 0.31 ng/g.The NEO concentrations in the water bodies across the Dongting Lake basin increased in the order of the Xiangjiang,Zishui,Yuanjiang,and Lishui rivers(collectively referred to as the Four Rivers),the mainstream of Dongting Lake,the Xinqiang River,the Miluo River,and the Hudu,Ouchi,and Songzi rivers(collectively referred to as the Three Outlets).Sediments from tributaries progressively accumulate in the lake.The ecological risk assessment identified IMI and DIN as the highest-risk compounds(RQ>1),with high-risk areas concentrated in the mainstream of Dongting Lake and the Ouchi,Miluo,and Hudu rivers.The fugacity model showed that IMI,ACE,and THIA are prone to diffuse from sediments to water bodies in most areas,with fugacity fractions(ff)values of greater than 0.5.In contrast,the mainstream of Dongting Lake acts as a sink of CLO and DIN(ff values:<0.5).Sediments at the lake’s outlet emerge as an important sink of NEOs.Based on the results of this study,it is advisable to strengthen the supervision of NEO applications in agricultural areas and to implement zonal control strategies.These measures will help reduce ecological risks and protect the safety of water ecosystems in the Dongting Lake region.
基金National Natural Science Foundation of China(Nos.U21A20291,42377384)National Key R&D Program of China(No.2021YFD1000500)Major Research Plan of the Shandong Science Foundation(No.ZR2020ZD19).
文摘The extensive use of neonicotinoids on food crops for pest management has resulted in substantial environmental contamination.It is imperative to develop an effective remediation material and technique as well as to determine the evolution pathways of products.Here,novel ball-milled nitrogen-doped biochar(NBC)-modified zero-valent iron(ZVI)composites(named MNBC-ZVI)were fabricated and applied to degrading neonicotinoids.Based on the characterization results,NBC incorporation introduced N-doped sites and new allying heterojunctions and achieved surface charge redistribution,rapid electron transfer,and higher hydrophobicity of ZVI particles.As a result,the interaction between ZVI particles and thiamethoxam(a typical neonicotinoid)was improved,and the adsorption-desorption and reductive degradation of thiamethoxam and·H generation steps were optimized.MNBC-ZVI could rapidly degrade 100%of 10 mg·L^(−1) thiamethoxam within 360 min,its reduction rate constant was 12.1-fold greater than that of pristine ZVI,and the electron efficiency increased from 29.7%to 57.8%.This improved reactivity and selectivity resulted from increased electron transfer,enhanced hydrophobicity,and reduced accumulation of iron mud.Moreover,the degradation of neonicotinoids occurred mainly via nitrate reduction and dichlorination,and toxicity tests with degradation intermediates revealed that neonicotinoids undergo rapid detoxification.Remarkably,MNBCZVI also presented favorable tolerance to various anions,humic acid,wastewater and contaminated soil,as well as high reusability.This work offers an efficient and economic biochar-ZVI remediation technology for the rapid degradation and detoxification of neonicotinoids,significantly contributes to knowledge on the relevant removal mechanism and further advances the synthesis of highly reactive and environmentally friendly materials.
文摘Thiacloprid has been banned in many European countries for its toxicity, but is nevertheless still used outside the EU. Using the ant Myrmica sabuleti as a model organism, we sought a concentration of thiacloprid that would be low in environmental impact, but nonetheless harmful to an insect. Assessed on ten biological traits, a sub-lethal 2 μg/L concentration in the sugar water diet of the ants impacted their locomotion and other motor-linked behavioral traits such as orientation, moving on an unfamiliar device, moving on a rough surface, brood caring and progressing along a twist and turns path. Sensory perception appeared unaffected. Behaviors involving cognition or related in some way to it, such as social relationships, ability to leave an enclosure, learning and memory also appeared unaffected, but their outcomes could be entangled with those of locomotor impairment. The effect of thiacloprid on locomotion vanished in about 30 hours. Adverse effects were still present with the 0.1 and 0.01 μg/L concentrations, but at a lower level. Partial physiological adaptation at the individual level occurred for the 2 μg/L concentration, less so for 0.1 μg/L and not for 0.01 μg/L. Thiacloprid should thus be used at the lowest still active concentration producing a significant damaging behavioral effect with no physiological adaptation. This concentration remains to be specifically defined for targeted pest species.
基金grants from the National Basic Research and Development Program of China(2009CB119200)the National Natural Science Foundation of China(31071683)
文摘Four strains of the Q biotype and one of the B biotype of the whitefly Bemisia tabaci collected from China were characterised for resistance to four neonicotinoid insecticides and pymetrozine.Q biotype strains showed moderate to strong resistance to imidacloprid,thiamethoxam and acetamiprid,but little or no cross-resistance to dinotefuron.Resistance to neonicotinoids was consistently associated with resistance to pymetrozine,despite the latter having a distinct（though unresolved）mode of action.The single B biotype strain proved largely susceptible to all the insecticides investigated.Resistance in the Q biotype strains was associated with over-expression of a cytochrome P450 monooxygenase gene,CYP6CM1,whose substrate specificity presumably accounts for the observed cross-resistance profiles.
基金supported by the China Scholarship Council oversea Ph D study program(No.201906850003)by the Exposome center of Excellence of the University of Antwerp(BOF grant,Antigoon ID no.41222)。
文摘Pyrethroids,organophosphorus pesticides and fipronil have been listed as priority chemicals in human biomonitoring studies because of their wide use and potential health effects in humans.The determination of 13 pesticides,including pyrethroids(deltamethrin,cypermethrin,permethrin,cyfluthrin,bifenthrin),organophosphorus(chlorpyrifos,chlorpyrifosmethyl,and malathion),fipronil,neonicotinoids(imidacloprid,acetamiprid and thiacloprid)and triazole(prothioconazole),together with 13 corresponding metabolites in human urine samples was achieved by solid-phase extraction and analysis by liquid chromatography coupled to tandem mass spectrometry.All targeted compounds,except malathion dicarboxylic acid,were measured with a mean within-accuracy(n=5)of 71%–114%(RSD:1%–14%)and between-run(n=15)accuracy of 80%–118%(RSD:2%–14%).Limits of quantitation of the targeted analytes ranged from 0.1 to 16 pg/m L.The detection result of urine samples from 25 volunteers indicated that the detection frequencies of 3,5,6-trichloro-2-pyridinol(median:448 pg/m L),6-chloropyridine-3-carboxylic acid(median:193 pg/m L),2-methyl-3-phenylbenzoic acid(median:181 pg/m L),3-phenoxybenzoic acid(median:99 pg/m L),2-isopropyl-6-methyl-4-pyrimidinol(median:77 pg/m L),cyfluthrin(median:59 pg/m L),cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid(cis-DCCA,median:53 pg/m L),trans-DCCA(median:25 pg/m L),prothioconazole(median:21 pg/m L),imidacloprid(median:7 pg/m L),and prothioconazole-desthio(median:1 pg/m L)were>50%.The obtained results show that the validated method is suitable for the human biomonitoring of these currentuse pesticides and their metabolites.
基金supported by National Key Technology R&D Program of China(No.2011BAE06B01)
文摘A series of new hexahydroimidazo[1,2-a]pyridine derivatives were synthesized via convenient and practical three-component reactions. Preliminary bioassays showed that majority of the target compounds exhibited moderate to excellent insecticidal activity against cowpea aphids （Aphis craccivora）. Among them, compound 91 demonstrated significant activity with LCso value of 0.00918 mmol/L which was about 3.8-fold higher than that of imidacloprid （IMI）. Furthermore, the study of stereostructure-activity relationship of four isomers of 9k indicated that configuration played a key role in insecticidal activity of these compounds.
文摘A series of novel neonicotinoids derivatives 4a―4p was designed and synthesized by introducing the ethylbenzene group into the thiazole ring, their structures were confirmed by IR, 1H NMR and elemental analysis. The crystal structure of compound 4j has been determined by X-ray diffraction analysis.
基金financial supported by National High Technology Research Development Program of China (863 Program, No. 2011AA10A207)National Natural Science Foundation of China (Nos. 21472046, 21372079)+2 种基金Shanghai Pujiang Program (No. 14PJD012)the Fundamental Research Funds for the Central Universities (No. 222201414015)partly supported by Australia DC Foundation
文摘A series of novel tetrahydroimidazo[1,2-a]pyridine-5（1H）-one derivatives containing a electronegative pharmacophore（=CNO_2） were synthesized via practical aza-ene reaction and characterized by ~1H NMR,^（13）C NMR,^（19）F NMR and HRMS. Preliminary bioassays showed that some of the target compounds exhibited good insecticidal activity against brown planthopper（Nilaparvata lugens） and cowpea aphids（Aphis craccivora） at 500 mg L^（-1）. Among them, compound 11 h was active against brown planthopper at100 mg L^（-1）. The insecticidal activities varied significantly depending on the types and patterns of the substituents, which provided guidance for further investigation on structure modifications.
文摘Alzheimer’s disease(AD)is a progressive and neurodegenerative illness which results in alterations in cognitive development.It is characterized by loss/dysfunction of cholinergic neurons,and formation of amyloid plaques,and formation of neurofibrillary tangles,among other changes,due to hyperphosphorylation of tau-protein.Exposure to pesticides in humans occurs frequently due to contact with contaminated food,water,or particles.Organochlorines,organophosphates,carbamates,pyrethroids and neonicotinoids are associated with the most diagnosed incidents of severe cognitive impairment.The aim of this study was to determine the effects of these pesticides on the phosphorylation of tau protein,and its cognitive implications in the development of AD.It was found that exposure to pesticides increased the phosphorylation of tau protein at sites Ser198,Ser199,Ser202,Thr205,Ser396 and Ser404.Contact with these chemicals altered the enzymatic activities of cyclin-dependent kinase 5 and glycogen synthase kinase 3 beta,and protein phosphatase-2A.Moreover,it altered the expression of the microtubule associated protein tau gene,and changed levels of intracellular calcium.These changes affected tau protein phosphorylation and neuroinflammation,and also increased oxidative stress.In addition,the exposed subjects had poor level of performance in tests that involved evaluation of novelty,as test on verbal,non-verbal,spatial memory,attention,and problem-solving skills.
