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
The photo-aging behavior of microplastics(MPs)in natural environment has become a global concern.The ultraviolet radiation has enough energy to change the polymer structure and physicalchemical properties of MPs.Less ...The photo-aging behavior of microplastics(MPs)in natural environment has become a global concern.The ultraviolet radiation has enough energy to change the polymer structure and physicalchemical properties of MPs.Less attention has focused on the interactions of the photo-aged polar and biodegradable MPs with organic pollutants.This work investigated the structural properties of aged polar polyamide(PA)MPs and biodegradable polylactic acid(PLA)MPs exposed to ultraviolet irradiation and their adsorption behavior and mechanism for neonicotinoid insecticide imidacloprid(IMI).The results showed that the MPs had extensive changes in surface morphology and chemical properties after photo-aging.The C–N bond of PA MPs was disrupted to form more carbonyl groups.The oxygen-containing functional groups on the surface of aged PLA MPs were broken and generated relatively smaller molecules.The adsorption capacity of IMI on PA MPs decreased by 19.2%,while the adsorption capacity of IMI on PLA MPs increased by 41.2%after photo-aging.This depended on the natural structure of the MPs and their ability to absorb ultraviolet light.The electrostatic interactions,hydrogen bonds,van der Waals interactions,and polar-polar interactions were the main adsorption mechanisms of IMI on MPs.High initial solution pH and low ionic strength favored the adsorption of IMI by altering charge distribution on the MPs surface.The formation of the humic acid-IMI complexes decreased the concentration of IMI in the water phase and further decreased the adsorption on MPs.These results are enlightening for a scientific comprehension of the environmental behavior of the polar MPs.展开更多
Chiral pollutants often pose significant differential environmental health risks.In this study,the biotransformation of chiral dinotefuran(DIN)and its enantioselective metabolic toxicity mechanisms have been systemica...Chiral pollutants often pose significant differential environmental health risks.In this study,the biotransformation of chiral dinotefuran(DIN)and its enantioselective metabolic toxicity mechanisms have been systemically investigated.Firstly,reversedphase chromatography-high resolution mass spectrometry was developed to quantify the content of DIN R/S chiral enantiomer with pg level sensitivity,revealing a lower elimination rate constant(K_(e))of S-DIN(0.730 h^(-1))than R-DIN(0.746 h^(-1)).Secondly,the interaction mechanism between DIN metabolism and important endogenous bioactive molecules,such as aldehyde oxidase(AOX)and neurotransmitters,was revealed.The DIN nitro-group was converted into a guanidine group by the reducing site of nearby flavin adenine dinucleotide(FAD)in AOX with the preferred higher affinity of S-configuration.Meanwhile,the endogenous tryptophan(Trp)aldehyde metabolic intermediate,5-hydroxyindoleacetaldehyde(5-HIAL),provides a persistent electron donor for DIN reduction via the oxidation-catalyzed site in AOX,resulting in remarkable up-regulation of monoamine neurotransmitters such as serotonin and dopamine.Thirdly,the higher level of neurotransmitters further mediated dysregulation of oxylipin homeostasis via the serotonergic pathway,where S-DIN exhibited more pronounced liver lipid damage and environmental health risk with the accumulated lipid biomarkers,oxidized triglyceride(OxTG)and oxidized sphingomyelin(OxSM).This study elucidates the AOX-mediated enantioselectivity metabolic pathway of DIN,providing a new analytical method for chiral pollutants and paves the way for their health risk assessments.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
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
Bemisia tabaci(Gennadius)(Hemiptera:Aleyrodidae)is a cosmopolitan insect pest causing serious damage to crop production.Cytochromes P450(CYPs)of B.tabaci are widely known to be involved in the metabolic resistance to ...Bemisia tabaci(Gennadius)(Hemiptera:Aleyrodidae)is a cosmopolitan insect pest causing serious damage to crop production.Cytochromes P450(CYPs)of B.tabaci are widely known to be involved in the metabolic resistance to a variety of insecticides,continuously increasing the difficulty in controlling this pest.In this study,four P450 genes(CYP6CMI,CYP6CXl,CYP6CX3,and CYP402CI)in B.tabaci exhibited correlations with the resistance to imidacloprid.We have focused on trying to understand the function and metabolism capacity of CYP402C1.The expression profiles of CYP402C1 were examined by reverse transcription quantitative real-time PCR and fluorescence in situ hybridizations.Its role in resistance to imidacloprid was investigated by RNA interference,transgenic Drosophila melanogaster,and heterologous expression.The results showed that CYP402CI was highly expressed in the active feeding stages of B.tabaci,such as nymphs and female adults.CYP402C1 was mainly expressed in midguts of nymphs and adults,especially in the filter chamber.Knockdown of CYP402CI significantly decreased the resistance of B.tabaci to imidacloprid by 3.96-fold(50%lethal concentration:186.46 versus 47.08 mg/L).Overexpression of CYP402CI in a transgenic D.melanogaster line(Gal4>UAS-CYP402CI)significantly increased the resistance to imidacloprid from 12.68-to 14.92-fold(129.01 and 151.80 mg/L versus 1925.14 mg/L).The heterologous expression of CYP402CI showed a metabolism ability of imidacloprid(imidacloprid decreased by 12.51%within 2 h).This study provides new insights for CYP402C1 function in B.tabaci and will help develop new strategies in B.tabaci control and its insecticide resistance.展开更多
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This work was supported by the National Natural Science Foundation of China(No.41977142)Major Science and Technology Program for Water Pollution Control and Treatment(No.2018ZX07111003).
文摘The photo-aging behavior of microplastics(MPs)in natural environment has become a global concern.The ultraviolet radiation has enough energy to change the polymer structure and physicalchemical properties of MPs.Less attention has focused on the interactions of the photo-aged polar and biodegradable MPs with organic pollutants.This work investigated the structural properties of aged polar polyamide(PA)MPs and biodegradable polylactic acid(PLA)MPs exposed to ultraviolet irradiation and their adsorption behavior and mechanism for neonicotinoid insecticide imidacloprid(IMI).The results showed that the MPs had extensive changes in surface morphology and chemical properties after photo-aging.The C–N bond of PA MPs was disrupted to form more carbonyl groups.The oxygen-containing functional groups on the surface of aged PLA MPs were broken and generated relatively smaller molecules.The adsorption capacity of IMI on PA MPs decreased by 19.2%,while the adsorption capacity of IMI on PLA MPs increased by 41.2%after photo-aging.This depended on the natural structure of the MPs and their ability to absorb ultraviolet light.The electrostatic interactions,hydrogen bonds,van der Waals interactions,and polar-polar interactions were the main adsorption mechanisms of IMI on MPs.High initial solution pH and low ionic strength favored the adsorption of IMI by altering charge distribution on the MPs surface.The formation of the humic acid-IMI complexes decreased the concentration of IMI in the water phase and further decreased the adsorption on MPs.These results are enlightening for a scientific comprehension of the environmental behavior of the polar MPs.
基金supported by the National Natural Science Foundation of China(22276076,22306074,22361132536,22236002)the Fundamental Research Funds for the Central Universities(JUSRP622032)the Jiangsu Association for Science and Technology Youth Science and Technology Talent Support Project(TJ2021-049)。
文摘Chiral pollutants often pose significant differential environmental health risks.In this study,the biotransformation of chiral dinotefuran(DIN)and its enantioselective metabolic toxicity mechanisms have been systemically investigated.Firstly,reversedphase chromatography-high resolution mass spectrometry was developed to quantify the content of DIN R/S chiral enantiomer with pg level sensitivity,revealing a lower elimination rate constant(K_(e))of S-DIN(0.730 h^(-1))than R-DIN(0.746 h^(-1)).Secondly,the interaction mechanism between DIN metabolism and important endogenous bioactive molecules,such as aldehyde oxidase(AOX)and neurotransmitters,was revealed.The DIN nitro-group was converted into a guanidine group by the reducing site of nearby flavin adenine dinucleotide(FAD)in AOX with the preferred higher affinity of S-configuration.Meanwhile,the endogenous tryptophan(Trp)aldehyde metabolic intermediate,5-hydroxyindoleacetaldehyde(5-HIAL),provides a persistent electron donor for DIN reduction via the oxidation-catalyzed site in AOX,resulting in remarkable up-regulation of monoamine neurotransmitters such as serotonin and dopamine.Thirdly,the higher level of neurotransmitters further mediated dysregulation of oxylipin homeostasis via the serotonergic pathway,where S-DIN exhibited more pronounced liver lipid damage and environmental health risk with the accumulated lipid biomarkers,oxidized triglyceride(OxTG)and oxidized sphingomyelin(OxSM).This study elucidates the AOX-mediated enantioselectivity metabolic pathway of DIN,providing a new analytical method for chiral pollutants and paves the way for their health risk assessments.
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.
基金supported by grants from the National Natural Science Foundation of China(32072456 and 31601659)the Science and Technology Supporting Program for Young Innovative Teams in Higher Education of Shandong Province(2020KJF001)the Taishan Scholar Foundation of Shandong Province(tsqn20161040).
文摘Bemisia tabaci(Gennadius)(Hemiptera:Aleyrodidae)is a cosmopolitan insect pest causing serious damage to crop production.Cytochromes P450(CYPs)of B.tabaci are widely known to be involved in the metabolic resistance to a variety of insecticides,continuously increasing the difficulty in controlling this pest.In this study,four P450 genes(CYP6CMI,CYP6CXl,CYP6CX3,and CYP402CI)in B.tabaci exhibited correlations with the resistance to imidacloprid.We have focused on trying to understand the function and metabolism capacity of CYP402C1.The expression profiles of CYP402C1 were examined by reverse transcription quantitative real-time PCR and fluorescence in situ hybridizations.Its role in resistance to imidacloprid was investigated by RNA interference,transgenic Drosophila melanogaster,and heterologous expression.The results showed that CYP402CI was highly expressed in the active feeding stages of B.tabaci,such as nymphs and female adults.CYP402C1 was mainly expressed in midguts of nymphs and adults,especially in the filter chamber.Knockdown of CYP402CI significantly decreased the resistance of B.tabaci to imidacloprid by 3.96-fold(50%lethal concentration:186.46 versus 47.08 mg/L).Overexpression of CYP402CI in a transgenic D.melanogaster line(Gal4>UAS-CYP402CI)significantly increased the resistance to imidacloprid from 12.68-to 14.92-fold(129.01 and 151.80 mg/L versus 1925.14 mg/L).The heterologous expression of CYP402CI showed a metabolism ability of imidacloprid(imidacloprid decreased by 12.51%within 2 h).This study provides new insights for CYP402C1 function in B.tabaci and will help develop new strategies in B.tabaci control and its insecticide resistance.
