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
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
Spiro heterocycles frequently occur in bioactive molecules. In the pursuit of neonicotinoids with spiro hererocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenon...Spiro heterocycles frequently occur in bioactive molecules. In the pursuit of neonicotinoids with spiro hererocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenone framework were designed and synthesized. Insecticidal evaluation showed that some of spirobenzofuranone containing neonicotinoids exhibited moderate activity against cowpea aphid, armyworm or brown planthopper.展开更多
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
An effective prediction pharmacophore model （RMS = 0.634, Correl = 0.893, Weight = 1.463, Config = 11.940） was successfully obtained by 3D-QSAR based on a series of nAChR （nicotinic acetylcholine receptors） agonis...An effective prediction pharmacophore model （RMS = 0.634, Correl = 0.893, Weight = 1.463, Config = 11.940） was successfully obtained by 3D-QSAR based on a series of nAChR （nicotinic acetylcholine receptors） agonists, which consists of a hydrogen- bonding acceptor, a hydrogen-bond donor, a hydrophobic aliphatic and a hydrophobic aromatic centre. This pharmacophore model may provide theoretical basis for designation and development of higher active insecticides.展开更多
Chlorothiazole ring, as a substituted heterocycle, frequently occurred in structures of various insecticides, and brought positive effect on bioactivity. In purpose to find novel neonicotinoids, a series of pyrrole- a...Chlorothiazole ring, as a substituted heterocycle, frequently occurred in structures of various insecticides, and brought positive effect on bioactivity. In purpose to find novel neonicotinoids, a series of pyrrole- and dihydropyrrole-fused neonicotinoid analogs containing chlorothiazole ring were synthesized for the first time. Results of the following biological assays showed that compounds Sa-c achieved good insecticidal activity against Aphis craccivora, and compound Sh exhibited good activity against Nilaparvata lugens.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
Ten new N-oxalyl derivatives of neonicotinoid compound were designed and synthesized. Their structures were confirmed by ^1H NMR spectra, elemental analysis and X-ray diffraction. The preliminary insecticidal activiti...Ten new N-oxalyl derivatives of neonicotinoid compound were designed and synthesized. Their structures were confirmed by ^1H NMR spectra, elemental analysis and X-ray diffraction. The preliminary insecticidal activities of the new compounds were evaluated. The results of bioassays indicate that the title Compounds exhibit moderate insecticidal activities. Surprisingly, the insecticidal activity of compound 7b against bean aphids at 200 mg/kg is 100%, which is comoarable to that of the commercialized imidacloprid.展开更多
A novel （Z）-nitromethylene neonicotinoid analogue （C23H27Cl2N5O4·2H2O） （II） with optical activity has been synthesized, the structure was characterized by elemental analysis, IR and 1H NMR spectra, and the ...A novel （Z）-nitromethylene neonicotinoid analogue （C23H27Cl2N5O4·2H2O） （II） with optical activity has been synthesized, the structure was characterized by elemental analysis, IR and 1H NMR spectra, and the （Z）-configuration was confirmed by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 7.4638（3）, b = 12.6232（5）, c = 15.2990（6）, α = 71.907（1）, β = 89.397（2）, γ = 80.314（1）°, V = 1349.28（9）3, Z = 2, Dc = 1.340 g/cm3, μ = 0.286 mm-1, Mr = 544.43, F（000） = 572, S = 1.056, R = 0.0801 and wR = 0.2366 for 4998 unique reflections with 3012 observed ones （I 〉 2σ（I））. In the crystal, the dihedral angle between the pyridine and 4-Cl-phenyl rings is 58.13°. Intermolecular O-H···O, C-H···O and C-H···Cl hydrogen bonds involving water molecules stabilize the crystal structure.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
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
Cowpea （Vigna unguiculata L. Walp.） and tomato （Lycopersicum esculentum L. Karst） are attacked by a wide range of insect pests worldwide. In many cases, pesticides are used to control the pests. In 2010 and 2011, ...Cowpea （Vigna unguiculata L. Walp.） and tomato （Lycopersicum esculentum L. Karst） are attacked by a wide range of insect pests worldwide. In many cases, pesticides are used to control the pests. In 2010 and 2011, we conducted field experiments to evaluate and compare the effectiveness of a biorational （Agroneem~） and conventional pesticide （imidacloprid or thiamethoxam） on insect pests of these crops. In the first year, two varieties of cowpea （Mississippi Silver and Pinkeye Purple Hull） and two of tomato （Mariana and German Johnson） were used; in the second year, the better performing of each group （Mississippi Silver and Mariana） were used for the study. A split-plot design with four replications in Year 1, and a randomized complete block design with six treatment combinations in Year 2. In the first year, both pesticide groups were applied following manufacturer＇s recommendation （10-14 d cycles）; and in the second year, the application of the pesticides was driven by economic thresholds level （ETL） of insect pests. The most prevalent species of insects recorded in both crops were in the families： Chrysomelidae, Pentatomidae, Cicadellidae, Vespidae, Sarcophagidae, Thripidae and Sphingidae. In both years, the diversity of insects on cowpea was greater than on tomato and more insects were observed in the second year compared to the first, despite the absence of significant difference （P 〉 0.05） between varieties in the treated plots. The yield of cowpea and tomato was comparable in all sprayed plots.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
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
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
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
Aphis gossypii Glover （Hemiptera： Aphididae） is a key pest in cotton crops, notably owing to its increasing resistance to commonly used pesticides. Such resistance prompts for the development of integrated pest man...Aphis gossypii Glover （Hemiptera： Aphididae） is a key pest in cotton crops, notably owing to its increasing resistance to commonly used pesticides. Such resistance prompts for the development of integrated pest management （IPM） programs that include novel pesticides being effective against the aphid. In the present study, we assessed lethal and sublethal effects of cycloxaprid, a novel chiral neonicotinoid pesticide developed in China, on A. gossypii. The lethal concentration at 50% （LCs0） value of cycloxaprid on A. gossypii was estimated, using the dipping method, at 7.73 mg/L. The impact of a sublethal concentration （LC10） and a lethal concentration （LC40） of cycloxaprid on A. gossypii population growth and feeding behavior （using electrical penetration graph technique [EPG]）, and its transgenerational effect were further assessed. Adult longevity and fecundity significantly decreased after exposure to LEa0 or LC10 of cycloxaprid. Cycloxaprid with sublethal concentrations （especially LC40） had negative effects on phloem ingestion by A. gossypii. Additionally, the offspring of the adults exposed to LC40 of cycloxaprid had shorter nymphal development duration and adult longevity than the control, and those from LC10 and LC40 treatments had lower adult fecundity and net productive rate. We demonstrated that cycloxaprid is a pesticide showing both lethal and sublethal activities, and transgenerational effects on,4. gossypii; it may be useful for implementation in IPM programs against this aphid pest.展开更多
Nilaparvata lugens and Sogatella furcifera are two primary planthoppers on rice throughout Asian countries and areas. Neonicotinoid insecticides, such as imidaclo- prid （IMI）, have been extensively used to control r...Nilaparvata lugens and Sogatella furcifera are two primary planthoppers on rice throughout Asian countries and areas. Neonicotinoid insecticides, such as imidaclo- prid （IMI）, have been extensively used to control rice planthoppers and IMI resistance consequently occurred with an important mechanism from the over-expression of P450 genes. The induction of P450 genes by IMI may increase the ability to metabolize this insecticide in planthoppers and increase the resistance risk. In this study, the induction of P450 genes was compared in S. furcifera treated with IM] and nitromethyleneimidazole （NMI）, in two planthopper species by IMI lethal dose that kills 85% of the population （LD85）, and in N. lugens among three IMI doses （LD15, LD50 and LD85）. When IMI and NMI at the LD85 dose were applied to S. furcifera, the expression changes in most P450 genes were similar, including the up-regulation of nine genes and down-regulation of three genes. In terms of the expression changes in 12 homologous P450 genes between N. lugens and S. furcifera treated with IMI at the LD85 dose, 10 genes had very similar patterns, such as up-regulation in seven genes, down-regulation in one gene and no significant changes in two genes. When three different IMI doses were applied to N. lugens, the changes in P450 gene expression were much different, such as up-regulation in four genes at all doses and dose-dependent regulation of the other nine genes. For example, CYP6AY1 could be induced by all IMI doses, while CYP6ER1 was only up-regulated by the LDs0 dose, although both genes were reported important in IMI resistance. In conclusion, P450 genes in two planthopper species showed similar regulation patterns in responding to IMI, and the two neonicotinoid insecticides had similar effects on P450 gene expression, although the regulation was often dose-dependent.展开更多
Neonicotinoid insecticides(NNIs)have been intensively used and exploited,resulting in their presence and accumulation in multiple environmental media.We herein investigated the current levels of eight major NNIs in th...Neonicotinoid insecticides(NNIs)have been intensively used and exploited,resulting in their presence and accumulation in multiple environmental media.We herein investigated the current levels of eight major NNIs in the Harbin section of the Songhua River in northeast China,providing the first systematic report on NNIs in this region.At least four NNIs in water and three in sediment were detected,with total concentrations ranging from 30.8 to 135 ng L^(-1) and from 0.61 to 14.7 ng g^(-1) dw,respectively.Larger spatial variations in surface water NNIs concentrations were observed in tributary than mainstream(p<0.05)due to the intensive human activities(e.g.,horticulture,urban landscaping,and household pet flea control)and the discharge of wastewater from many treatment plants.There was a significant positive correlation(p<0.05)between the concentrations of residual imidacloprid(IMI),clothianidin(CLO),and S4NNIs in the sediment and total organic carbon(TOC).Due to its high solubility and low octanol-water partition coefficient(Kow),the sediment-water exchange behavior shows that NNIs in sediments can re-enter into the water body.Human exposure risk was assessed using the relative potency factor(RPF),which showed that infants have the highest exposure risk(estimated daily intake(SIMIeq EDI):31.9 ng kg^(-1) bw$d^(-1)).The concentration thresholds of NNIs for aquatic organisms in the Harbin section of the Songhua River were determined using the species sensitivity distribution(SSD)approach,resulting in a value of 355 ng L^(-1) for acute hazardous concentration for 5%of species(HC5)and 165 ng L^(-1) for chronic HC5.Aquatic organisms at low trophic levels were more vulnerable to potential harm from NNIs.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
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financial supported by National Basic Research Program of China(973 Program,No.2010CB126100)National High Technology Research Development Program of China(863 Program,No.2011AA10A207)+4 种基金Key Projects in the National Science & Technology Pillar Program(No.2011BAE06B05)National Natural Science Foundation of China(No.21372079)Shanghai Education Committee(No.12ZZ057)the Fundamental Research Funds for the Central Universitiespartly supported by Australia DC Foundation
文摘Spiro heterocycles frequently occur in bioactive molecules. In the pursuit of neonicotinoids with spiro hererocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenone framework were designed and synthesized. Insecticidal evaluation showed that some of spirobenzofuranone containing neonicotinoids exhibited moderate activity against cowpea aphid, armyworm or brown planthopper.
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.
文摘An effective prediction pharmacophore model （RMS = 0.634, Correl = 0.893, Weight = 1.463, Config = 11.940） was successfully obtained by 3D-QSAR based on a series of nAChR （nicotinic acetylcholine receptors） agonists, which consists of a hydrogen- bonding acceptor, a hydrogen-bond donor, a hydrophobic aliphatic and a hydrophobic aromatic centre. This pharmacophore model may provide theoretical basis for designation and development of higher active insecticides.
基金supported by National Key Technology R&D Program of China(No.2011BAE06B01)
文摘Chlorothiazole ring, as a substituted heterocycle, frequently occurred in structures of various insecticides, and brought positive effect on bioactivity. In purpose to find novel neonicotinoids, a series of pyrrole- and dihydropyrrole-fused neonicotinoid analogs containing chlorothiazole ring were synthesized for the first time. Results of the following biological assays showed that compounds Sa-c achieved good insecticidal activity against Aphis craccivora, and compound Sh exhibited good activity against Nilaparvata lugens.
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.
文摘Ten new N-oxalyl derivatives of neonicotinoid compound were designed and synthesized. Their structures were confirmed by ^1H NMR spectra, elemental analysis and X-ray diffraction. The preliminary insecticidal activities of the new compounds were evaluated. The results of bioassays indicate that the title Compounds exhibit moderate insecticidal activities. Surprisingly, the insecticidal activity of compound 7b against bean aphids at 200 mg/kg is 100%, which is comoarable to that of the commercialized imidacloprid.
基金supported from the Key Laboratory of Rare Earth Functional Materials of Shanghai (07dz22303)the Key Scientific and Technological Project of Shanghai (09391912100)
文摘A novel （Z）-nitromethylene neonicotinoid analogue （C23H27Cl2N5O4·2H2O） （II） with optical activity has been synthesized, the structure was characterized by elemental analysis, IR and 1H NMR spectra, and the （Z）-configuration was confirmed by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 7.4638（3）, b = 12.6232（5）, c = 15.2990（6）, α = 71.907（1）, β = 89.397（2）, γ = 80.314（1）°, V = 1349.28（9）3, Z = 2, Dc = 1.340 g/cm3, μ = 0.286 mm-1, Mr = 544.43, F（000） = 572, S = 1.056, R = 0.0801 and wR = 0.2366 for 4998 unique reflections with 3012 observed ones （I 〉 2σ（I））. In the crystal, the dihedral angle between the pyridine and 4-Cl-phenyl rings is 58.13°. Intermolecular O-H···O, C-H···O and C-H···Cl hydrogen bonds involving water molecules stabilize the crystal structure.
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.
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.
文摘Cowpea （Vigna unguiculata L. Walp.） and tomato （Lycopersicum esculentum L. Karst） are attacked by a wide range of insect pests worldwide. In many cases, pesticides are used to control the pests. In 2010 and 2011, we conducted field experiments to evaluate and compare the effectiveness of a biorational （Agroneem~） and conventional pesticide （imidacloprid or thiamethoxam） on insect pests of these crops. In the first year, two varieties of cowpea （Mississippi Silver and Pinkeye Purple Hull） and two of tomato （Mariana and German Johnson） were used; in the second year, the better performing of each group （Mississippi Silver and Mariana） were used for the study. A split-plot design with four replications in Year 1, and a randomized complete block design with six treatment combinations in Year 2. In the first year, both pesticide groups were applied following manufacturer＇s recommendation （10-14 d cycles）; and in the second year, the application of the pesticides was driven by economic thresholds level （ETL） of insect pests. The most prevalent species of insects recorded in both crops were in the families： Chrysomelidae, Pentatomidae, Cicadellidae, Vespidae, Sarcophagidae, Thripidae and Sphingidae. In both years, the diversity of insects on cowpea was greater than on tomato and more insects were observed in the second year compared to the first, despite the absence of significant difference （P 〉 0.05） between varieties in the treated plots. The yield of cowpea and tomato was comparable in all sprayed plots.
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.
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.
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.
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.
文摘Aphis gossypii Glover （Hemiptera： Aphididae） is a key pest in cotton crops, notably owing to its increasing resistance to commonly used pesticides. Such resistance prompts for the development of integrated pest management （IPM） programs that include novel pesticides being effective against the aphid. In the present study, we assessed lethal and sublethal effects of cycloxaprid, a novel chiral neonicotinoid pesticide developed in China, on A. gossypii. The lethal concentration at 50% （LCs0） value of cycloxaprid on A. gossypii was estimated, using the dipping method, at 7.73 mg/L. The impact of a sublethal concentration （LC10） and a lethal concentration （LC40） of cycloxaprid on A. gossypii population growth and feeding behavior （using electrical penetration graph technique [EPG]）, and its transgenerational effect were further assessed. Adult longevity and fecundity significantly decreased after exposure to LEa0 or LC10 of cycloxaprid. Cycloxaprid with sublethal concentrations （especially LC40） had negative effects on phloem ingestion by A. gossypii. Additionally, the offspring of the adults exposed to LC40 of cycloxaprid had shorter nymphal development duration and adult longevity than the control, and those from LC10 and LC40 treatments had lower adult fecundity and net productive rate. We demonstrated that cycloxaprid is a pesticide showing both lethal and sublethal activities, and transgenerational effects on,4. gossypii; it may be useful for implementation in IPM programs against this aphid pest.
基金We thank Dr. David Nelson （Department of Molecular Science, University of Tennessee, Memphis, TN, USA） and the P450 nomenclature committee for naming full-length P450s identified in this study. This study was funded by National Natural Science Foundation of China （31322045 and 31130045） and Jiangsu Science Fund for Distinguished Young Scholars （BK20130028）.
文摘Nilaparvata lugens and Sogatella furcifera are two primary planthoppers on rice throughout Asian countries and areas. Neonicotinoid insecticides, such as imidaclo- prid （IMI）, have been extensively used to control rice planthoppers and IMI resistance consequently occurred with an important mechanism from the over-expression of P450 genes. The induction of P450 genes by IMI may increase the ability to metabolize this insecticide in planthoppers and increase the resistance risk. In this study, the induction of P450 genes was compared in S. furcifera treated with IM] and nitromethyleneimidazole （NMI）, in two planthopper species by IMI lethal dose that kills 85% of the population （LD85）, and in N. lugens among three IMI doses （LD15, LD50 and LD85）. When IMI and NMI at the LD85 dose were applied to S. furcifera, the expression changes in most P450 genes were similar, including the up-regulation of nine genes and down-regulation of three genes. In terms of the expression changes in 12 homologous P450 genes between N. lugens and S. furcifera treated with IMI at the LD85 dose, 10 genes had very similar patterns, such as up-regulation in seven genes, down-regulation in one gene and no significant changes in two genes. When three different IMI doses were applied to N. lugens, the changes in P450 gene expression were much different, such as up-regulation in four genes at all doses and dose-dependent regulation of the other nine genes. For example, CYP6AY1 could be induced by all IMI doses, while CYP6ER1 was only up-regulated by the LDs0 dose, although both genes were reported important in IMI resistance. In conclusion, P450 genes in two planthopper species showed similar regulation patterns in responding to IMI, and the two neonicotinoid insecticides had similar effects on P450 gene expression, although the regulation was often dose-dependent.
基金This work was supported by the National Natural Science Foundation of China(No.51779047)the Excellent Youth Science Foundation of Heilongjiang Province(YQ2019E001).
文摘Neonicotinoid insecticides(NNIs)have been intensively used and exploited,resulting in their presence and accumulation in multiple environmental media.We herein investigated the current levels of eight major NNIs in the Harbin section of the Songhua River in northeast China,providing the first systematic report on NNIs in this region.At least four NNIs in water and three in sediment were detected,with total concentrations ranging from 30.8 to 135 ng L^(-1) and from 0.61 to 14.7 ng g^(-1) dw,respectively.Larger spatial variations in surface water NNIs concentrations were observed in tributary than mainstream(p<0.05)due to the intensive human activities(e.g.,horticulture,urban landscaping,and household pet flea control)and the discharge of wastewater from many treatment plants.There was a significant positive correlation(p<0.05)between the concentrations of residual imidacloprid(IMI),clothianidin(CLO),and S4NNIs in the sediment and total organic carbon(TOC).Due to its high solubility and low octanol-water partition coefficient(Kow),the sediment-water exchange behavior shows that NNIs in sediments can re-enter into the water body.Human exposure risk was assessed using the relative potency factor(RPF),which showed that infants have the highest exposure risk(estimated daily intake(SIMIeq EDI):31.9 ng kg^(-1) bw$d^(-1)).The concentration thresholds of NNIs for aquatic organisms in the Harbin section of the Songhua River were determined using the species sensitivity distribution(SSD)approach,resulting in a value of 355 ng L^(-1) for acute hazardous concentration for 5%of species(HC5)and 165 ng L^(-1) for chronic HC5.Aquatic organisms at low trophic levels were more vulnerable to potential harm from NNIs.
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.
