Developing an excellent photocatalysis system to remove pesticides from water is an urgent problem in current environment purification field.Herein,a Z-scheme WO_(3)/g-C_(3)N_(4) photocatalyst was prepared by a facile...Developing an excellent photocatalysis system to remove pesticides from water is an urgent problem in current environment purification field.Herein,a Z-scheme WO_(3)/g-C_(3)N_(4) photocatalyst was prepared by a facile in-situ calcination method,and the photocatalytic activity was investigated for degradation of nitenpyram(NTP)under visible light.The optimal Z-scheme WO_(3)/g-C_(3)N_(4) photocatalyst displayed the highest rate constant(0.036 min-1),which is about 1.7 and 25 times higher than that of pure g-C_(3)N_(4) and WO_(3),respectively.The improvement of photocatalytic performance is attributed to fast transfer of photogene rated carriers in the Z-scheme structure,which are testified by electron spin resonance(ESR)experiments,photocurrent and electrochemical impedance spectra(EIS)measurements.Moreover,the effects of typical water environmental factors on the degradation NTP were systematically studied.And the possible degradation pathways of NTP were deduced by the intermediates detected by highperformance liquid chro matography-mass spectrometry(HPLC-MS).This work will not only contribute to understand the degradation mechanism of pesticides in real water environmental condition,but also promote the development of new technologies for pesticide pollution control as well as environmental remediation.展开更多
As a common insecticide,nitenpyram(NTP)seriously threatens the human health and environmental safety.In this work,a visible-light-responsive photocata-lyst two-dimensional(2D)Bi_(2)WO_(6) was synthesized and applied t...As a common insecticide,nitenpyram(NTP)seriously threatens the human health and environmental safety.In this work,a visible-light-responsive photocata-lyst two-dimensional(2D)Bi_(2)WO_(6) was synthesized and applied to degrade NTP.Compared with bulk Bi_(2)WO_(6),the 2D Bi_(2)WO_(6)exhibits better photocatalytic performance for NTP degradation under visible-light irradiation.The enhanced activity can be ascribed to the unique 2D struc-ture which would induce to higher efficiency of carrier separation.Moreover,hole(h+)plays a major role(and·O^(2-))in the degradation of NTP.Based on the interme-diates detected by high-performance liquid chromatogra-phy-mass spectrometry(HPLC-MS),the degradation pathway of NTP was proposed.In addition,the influence of typical environmental factors(pH,water matrix,inorganic cations and common anions)on the degradation of NTP was also investigated.This work not only helps people to understand the degradation of pesticides in actual water bodies,but also provides reference for the subsequent treatment of agricultural wastewater.展开更多
Several studies have confirmed that the health status of the paternal affects the health of the offspring,however,it remains unknown whether paternal exposure to pesticides affect the offspring health.Here,we used unt...Several studies have confirmed that the health status of the paternal affects the health of the offspring,however,it remains unknown whether paternal exposure to pesticides affect the offspring health.Here,we used untargeted metabolomics and 16S rRNA sequencing technology,combined with tail suspension test and RT-qPCR to explore the effects of paternal exposure to nitenpyram on the neurotoxicity of offspring.Our results found that the paternal exposure to nitenpyram led to the offspring’s depressive-like behaviors,accompanied by the reduction of tryptophan content and the disorder of microbial abundance in the gut of the offspring.Further,we determined the expression of tryptophan metabolism-related genes tryptophanase(tnaA)and tryptophan hydroxylase 1(TpH1)in gut bacteria and colonic tissues.We found that tryptophan is metabolized to indoles rather than being absorbed into colonocytes,which coursed the reduce of tryptophan availability after nitenpyram exposure.In conclusion,our study deepens our understanding of the intergenerational toxic effects of pesticides.展开更多
[Objective] The paper was to establish a HPLC method for quantitative determination of 80% pymetrozine·nitenpyram WG. [Method] With the mixture of acetonitrile, water and phosphate buffer （volume ratio 10：80...[Objective] The paper was to establish a HPLC method for quantitative determination of 80% pymetrozine·nitenpyram WG. [Method] With the mixture of acetonitrile, water and phosphate buffer （volume ratio 10：80：10） as the mobile phase, pymetrozine and nitenpyram in samples were separated by ODS-2 reversed phase column, and detected by UV detector at 250 nm. In addition, the results were quantified by external standard method. [Result] The linear correlation coefficients of pymetrozine and nitenpyram were 0.9995 and 0.9998; the standard deviations were 0.29 and 0.22; the coefficients of variation were 0.51% and 1.21%; and the average recoveries were 100.7% and 99.1%, respectively. [Conclusion] The method is fast and simple, and can effectively separate pymetrozine and nitenpyram, with high precision and accuracy and good linear relation.展开更多
In this study,a fluorenyl pyridine-based(FPD)conjugated polymer was synthesized and used as a fluorescent probe to e fficiently and rapidly detect nitenpyram(NIT).NIT can quench the fluorescence of FPD,and the quenchi...In this study,a fluorenyl pyridine-based(FPD)conjugated polymer was synthesized and used as a fluorescent probe to e fficiently and rapidly detect nitenpyram(NIT).NIT can quench the fluorescence of FPD,and the quenching e fficiency can reach up to 82.75%.The linear ranges of NIT detection in ethanol-phosphate buff ered saline and ethanol were 0-64μM and 0-45μM,respectively,and the detection limit was as low as 0.62μM.FPD has good selective recognition and antiinterference abilities for NIT.Combined with a study on the fluorescence spectral anisotropy of FPD and NIT,the mechanism of the reaction between FPD and NIT was explored.It was concluded that FPD and NIT quenched their fluorescence under the combined action ofπ-πstacking and hydrogen bonding.Finally,NIT was recovered in organic cabbage,and the recovery rates were between 91.60%and 110.21%.The relative standard deviation was within 3.84%,indicating that FPD had high accuracy and good repeatability for the quantitative detection of NIT,further proving the feasibility of the fluorescence sensing method in practical applications.展开更多
Carboxylesterases(CarEs)represent one of the major detoxification enzyme families involved in insecticide resistance.However,the function of specific CarE genes in insecticide resistance is still unclear in the insect...Carboxylesterases(CarEs)represent one of the major detoxification enzyme families involved in insecticide resistance.However,the function of specific CarE genes in insecticide resistance is still unclear in the insect Nilaparvata lugens(Stål),a notorious rice crop pest in Asia.In this study,a total of 29 putative CarE genes in N.lugens were identified,and they were divided into seven clades;further,theβ-esterase clade was significantly expanded.Tissue-specific expression analysis found that 17 CarE genes were abundantly distributed in the midgut and fat body,while 12 CarE genes were highly expressed in the head.The expression of most CarE genes was significantly induced in response to the challenge of nitenpyram,triflumezopyrim,chlorpyrifos,isoprocarb and etofenprox.Among these,the expression levels of NlCarE2,NlCarE4,NlCarE9,NlCarE17 and NlCarE24 were increased by each insecticide.Real-time quantitative polymerase chain reaction and RNA interference assays revealed the NlCarE1 gene to be a candidate gene mainly involved in nitenpyram resistance,while simultaneously silencing NlCarE1 and NlCarE19 produced a stronger effect than silencing either one individually,suggesting a cooperative relationship in resistance formation.These findings lay the foundation for further clarification of insecticide resistance mediated by CarE in N.lugens.展开更多
The evolution of nitenpyram resistance has been confirmed to be related to overexpression of two key metabolic enzyme genes, CYP6ER1 and CarE1, in Nilaparvata lugens, a highly destructive rice pest that causes substan...The evolution of nitenpyram resistance has been confirmed to be related to overexpression of two key metabolic enzyme genes, CYP6ER1 and CarE1, in Nilaparvata lugens, a highly destructive rice pest that causes substantial economic losses and has developed insecticide resistance. As microRNAs (miRNAs) are important post-transcriptional regulators of gene expression, whether they are involved in nitenpyram resistance is poorly understood in N. lugens. In this study, knockdown of key genes in the miRNA biogenesis pathway (Dicer1, Drosha, and Argonaute1) changed CYP6ER1 and CarE1 abundance, which confirmed the importance of miRNAs in nitenpyram resistance. Furthermore, global screening of miRNAs associated with nitenpyram resistance in N. lugens was performed, and a total of 42 known and 178 novel miRNAs were identified;of these, 57 were differentially expressed between the susceptible and resistant strains, and two (novel_85 and novel_191) were predicted to target CYP6ER1 and CarE1, respectively. Luciferase reporter assays demonstrated that novel_85 and novel_191 bind to the CYP6ER1 and CarE1 coding regions, respectively, and downregulate their expression. Moreover, modulating novel_85 and novel_191 expression by injection of miRNA inhibitors and mimics significantly altered N. lugens nitenpyram susceptibility. This is the first study to systematically screen and identify miRNAs associated with N. lugens nitenpyram resistance, and provides important information that can be used to develop new miRNA-based targets in insecticide resistance management.展开更多
This work demonstrated that Enteromorpha biochar with introduced iron(SFB900-3)could activate peroxymonosulfate(PMS)efficiently for NTP remediation.It removed 83.9%-95.1%of NTP in 60 min under a wide pH range from 3.1...This work demonstrated that Enteromorpha biochar with introduced iron(SFB900-3)could activate peroxymonosulfate(PMS)efficiently for NTP remediation.It removed 83.9%-95.1%of NTP in 60 min under a wide pH range from 3.15 to 8.95.Density functional theory(DFT)calculations revealed the synergistic relationship between internal Fe single atoms and introduced Fe compounds—Fe_(3)C.The adsorption capacity of SFB900-3 for persulfate improved from−0.953 eV to−4.214 eV,and the Bader charge analysis showed that Fe atoms as active sites(0.658 e)enhanced the adsorption capacity more than carbon(0.050 e).Moreover,the energy barrier for PMS dissociation reduced from 0.072 eV to−5.372 eV due to the longer length of O-O bond under the synergistic effect of Fe single atom and Fe_(3)C which increased from 1.467Åto 3.890ÅThe quenching experiment confirmed that ^(1)O_(2) was the main active substance in NTP degradation and its contribution rate was 88.2%,which was further verified by EPR detection.The effect factor experiments proved that the SFB900-3/PMS system had stable and efficient activity for NTP removal,which remained at 73.6%removal rate after three rounds of tests.This work provided novel guidance for constructing efficient and stable biochar-based materials for organic pollutant remediation.展开更多
A novel series of cb-nitenpyram analogues （2a--2p） were designed and prepared by introducing the 1,4-dihydropyridine, with their eis-configuration confirmed by X-ray diffraction. Preliminary bioassays showed that mo...A novel series of cb-nitenpyram analogues （2a--2p） were designed and prepared by introducing the 1,4-dihydropyridine, with their eis-configuration confirmed by X-ray diffraction. Preliminary bioassays showed that most compounds exhibited good insecticidal activities at 20 mg/L against Aphis medicagini, and analogues 2a and 2d aflbrded the best activity, and both of them had 100% mortality at 4 mg/L. In addition, molecular docking studies were also performed to model the ligand-receptor complexes, and the results explained the structure-activity relationships observed in vitro, which may provide some useful information for future design of new insecticides.展开更多
基金financially supported by the National Science Funds for Creative Research Groups of China(No.51421006)National Natural Science Foundation of China(No.51679063)+2 种基金the Key Program of National Natural Science Foundation of China(No.91647206)the National key Plan for Research and Development of China(No.2016YFC0502203)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(No.51479064)。
文摘Developing an excellent photocatalysis system to remove pesticides from water is an urgent problem in current environment purification field.Herein,a Z-scheme WO_(3)/g-C_(3)N_(4) photocatalyst was prepared by a facile in-situ calcination method,and the photocatalytic activity was investigated for degradation of nitenpyram(NTP)under visible light.The optimal Z-scheme WO_(3)/g-C_(3)N_(4) photocatalyst displayed the highest rate constant(0.036 min-1),which is about 1.7 and 25 times higher than that of pure g-C_(3)N_(4) and WO_(3),respectively.The improvement of photocatalytic performance is attributed to fast transfer of photogene rated carriers in the Z-scheme structure,which are testified by electron spin resonance(ESR)experiments,photocurrent and electrochemical impedance spectra(EIS)measurements.Moreover,the effects of typical water environmental factors on the degradation NTP were systematically studied.And the possible degradation pathways of NTP were deduced by the intermediates detected by highperformance liquid chro matography-mass spectrometry(HPLC-MS).This work will not only contribute to understand the degradation mechanism of pesticides in real water environmental condition,but also promote the development of new technologies for pesticide pollution control as well as environmental remediation.
基金financially supported by the National Natural Science Foundation of China (No. 51979081)the Fundamental Research Funds for the Central Universities (No. B200202103)+1 种基金the National Key Plan for Research and Development of China (No. 2016YFC0502203)the National Science Funds for Creative Research Groups of China (No. 51421006) and PAPD
文摘As a common insecticide,nitenpyram(NTP)seriously threatens the human health and environmental safety.In this work,a visible-light-responsive photocata-lyst two-dimensional(2D)Bi_(2)WO_(6) was synthesized and applied to degrade NTP.Compared with bulk Bi_(2)WO_(6),the 2D Bi_(2)WO_(6)exhibits better photocatalytic performance for NTP degradation under visible-light irradiation.The enhanced activity can be ascribed to the unique 2D struc-ture which would induce to higher efficiency of carrier separation.Moreover,hole(h+)plays a major role(and·O^(2-))in the degradation of NTP.Based on the interme-diates detected by high-performance liquid chromatogra-phy-mass spectrometry(HPLC-MS),the degradation pathway of NTP was proposed.In addition,the influence of typical environmental factors(pH,water matrix,inorganic cations and common anions)on the degradation of NTP was also investigated.This work not only helps people to understand the degradation of pesticides in actual water bodies,but also provides reference for the subsequent treatment of agricultural wastewater.
基金supported by the National Key Research and Development Program of China (No.2016YFD0200202)the 2115 Talent Development Program of China Agricultural Universitythe Fundamental Research Program of Shanxi Province (No.20210302124131)。
文摘Several studies have confirmed that the health status of the paternal affects the health of the offspring,however,it remains unknown whether paternal exposure to pesticides affect the offspring health.Here,we used untargeted metabolomics and 16S rRNA sequencing technology,combined with tail suspension test and RT-qPCR to explore the effects of paternal exposure to nitenpyram on the neurotoxicity of offspring.Our results found that the paternal exposure to nitenpyram led to the offspring’s depressive-like behaviors,accompanied by the reduction of tryptophan content and the disorder of microbial abundance in the gut of the offspring.Further,we determined the expression of tryptophan metabolism-related genes tryptophanase(tnaA)and tryptophan hydroxylase 1(TpH1)in gut bacteria and colonic tissues.We found that tryptophan is metabolized to indoles rather than being absorbed into colonocytes,which coursed the reduce of tryptophan availability after nitenpyram exposure.In conclusion,our study deepens our understanding of the intergenerational toxic effects of pesticides.
文摘[Objective] The paper was to establish a HPLC method for quantitative determination of 80% pymetrozine·nitenpyram WG. [Method] With the mixture of acetonitrile, water and phosphate buffer （volume ratio 10：80：10） as the mobile phase, pymetrozine and nitenpyram in samples were separated by ODS-2 reversed phase column, and detected by UV detector at 250 nm. In addition, the results were quantified by external standard method. [Result] The linear correlation coefficients of pymetrozine and nitenpyram were 0.9995 and 0.9998; the standard deviations were 0.29 and 0.22; the coefficients of variation were 0.51% and 1.21%; and the average recoveries were 100.7% and 99.1%, respectively. [Conclusion] The method is fast and simple, and can effectively separate pymetrozine and nitenpyram, with high precision and accuracy and good linear relation.
文摘In this study,a fluorenyl pyridine-based(FPD)conjugated polymer was synthesized and used as a fluorescent probe to e fficiently and rapidly detect nitenpyram(NIT).NIT can quench the fluorescence of FPD,and the quenching e fficiency can reach up to 82.75%.The linear ranges of NIT detection in ethanol-phosphate buff ered saline and ethanol were 0-64μM and 0-45μM,respectively,and the detection limit was as low as 0.62μM.FPD has good selective recognition and antiinterference abilities for NIT.Combined with a study on the fluorescence spectral anisotropy of FPD and NIT,the mechanism of the reaction between FPD and NIT was explored.It was concluded that FPD and NIT quenched their fluorescence under the combined action ofπ-πstacking and hydrogen bonding.Finally,NIT was recovered in organic cabbage,and the recovery rates were between 91.60%and 110.21%.The relative standard deviation was within 3.84%,indicating that FPD had high accuracy and good repeatability for the quantitative detection of NIT,further proving the feasibility of the fluorescence sensing method in practical applications.
基金This study was supported by grants from the National Key Research and Development Program of China(2016YFD0200500)the National Natural Science Foundation of China(31871989 and 31471795).
文摘Carboxylesterases(CarEs)represent one of the major detoxification enzyme families involved in insecticide resistance.However,the function of specific CarE genes in insecticide resistance is still unclear in the insect Nilaparvata lugens(Stål),a notorious rice crop pest in Asia.In this study,a total of 29 putative CarE genes in N.lugens were identified,and they were divided into seven clades;further,theβ-esterase clade was significantly expanded.Tissue-specific expression analysis found that 17 CarE genes were abundantly distributed in the midgut and fat body,while 12 CarE genes were highly expressed in the head.The expression of most CarE genes was significantly induced in response to the challenge of nitenpyram,triflumezopyrim,chlorpyrifos,isoprocarb and etofenprox.Among these,the expression levels of NlCarE2,NlCarE4,NlCarE9,NlCarE17 and NlCarE24 were increased by each insecticide.Real-time quantitative polymerase chain reaction and RNA interference assays revealed the NlCarE1 gene to be a candidate gene mainly involved in nitenpyram resistance,while simultaneously silencing NlCarE1 and NlCarE19 produced a stronger effect than silencing either one individually,suggesting a cooperative relationship in resistance formation.These findings lay the foundation for further clarification of insecticide resistance mediated by CarE in N.lugens.
基金This study was supported by grants from the National Natural Science Foundation of China(31871989).
文摘The evolution of nitenpyram resistance has been confirmed to be related to overexpression of two key metabolic enzyme genes, CYP6ER1 and CarE1, in Nilaparvata lugens, a highly destructive rice pest that causes substantial economic losses and has developed insecticide resistance. As microRNAs (miRNAs) are important post-transcriptional regulators of gene expression, whether they are involved in nitenpyram resistance is poorly understood in N. lugens. In this study, knockdown of key genes in the miRNA biogenesis pathway (Dicer1, Drosha, and Argonaute1) changed CYP6ER1 and CarE1 abundance, which confirmed the importance of miRNAs in nitenpyram resistance. Furthermore, global screening of miRNAs associated with nitenpyram resistance in N. lugens was performed, and a total of 42 known and 178 novel miRNAs were identified;of these, 57 were differentially expressed between the susceptible and resistant strains, and two (novel_85 and novel_191) were predicted to target CYP6ER1 and CarE1, respectively. Luciferase reporter assays demonstrated that novel_85 and novel_191 bind to the CYP6ER1 and CarE1 coding regions, respectively, and downregulate their expression. Moreover, modulating novel_85 and novel_191 expression by injection of miRNA inhibitors and mimics significantly altered N. lugens nitenpyram susceptibility. This is the first study to systematically screen and identify miRNAs associated with N. lugens nitenpyram resistance, and provides important information that can be used to develop new miRNA-based targets in insecticide resistance management.
基金National Natural Science Foundation of China(Grant No.52270156,51909089)Natural Science Foundation of Hunan Province,China(Grant No.2020JJ5252)Training Program for Excellent Young Innovators of Changsha(Grant No.kq2209015).
文摘This work demonstrated that Enteromorpha biochar with introduced iron(SFB900-3)could activate peroxymonosulfate(PMS)efficiently for NTP remediation.It removed 83.9%-95.1%of NTP in 60 min under a wide pH range from 3.15 to 8.95.Density functional theory(DFT)calculations revealed the synergistic relationship between internal Fe single atoms and introduced Fe compounds—Fe_(3)C.The adsorption capacity of SFB900-3 for persulfate improved from−0.953 eV to−4.214 eV,and the Bader charge analysis showed that Fe atoms as active sites(0.658 e)enhanced the adsorption capacity more than carbon(0.050 e).Moreover,the energy barrier for PMS dissociation reduced from 0.072 eV to−5.372 eV due to the longer length of O-O bond under the synergistic effect of Fe single atom and Fe_(3)C which increased from 1.467Åto 3.890ÅThe quenching experiment confirmed that ^(1)O_(2) was the main active substance in NTP degradation and its contribution rate was 88.2%,which was further verified by EPR detection.The effect factor experiments proved that the SFB900-3/PMS system had stable and efficient activity for NTP removal,which remained at 73.6%removal rate after three rounds of tests.This work provided novel guidance for constructing efficient and stable biochar-based materials for organic pollutant remediation.
基金Supporting information for this article is available on the WWW under http：//dx.doi.org/10.1002/cjoc.201200165.Acknowledgement This work was supported by the National Natural Science Foundation of China （21042010, 21102092 and 30870560）, the Key Scientific ＂Twelfth Five-Year＂ National Technology Support Program （2011BAE06B0117）, the Innovation Project of Shanghai Education Commission （12YZ078）, the Leading Academic Discipline Project of Shanghai Normal University （DZL808）, Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University （07dz22303）. We are also grateful for the support from Branch of National Pesticide R＆D South Center.
文摘A novel series of cb-nitenpyram analogues （2a--2p） were designed and prepared by introducing the 1,4-dihydropyridine, with their eis-configuration confirmed by X-ray diffraction. Preliminary bioassays showed that most compounds exhibited good insecticidal activities at 20 mg/L against Aphis medicagini, and analogues 2a and 2d aflbrded the best activity, and both of them had 100% mortality at 4 mg/L. In addition, molecular docking studies were also performed to model the ligand-receptor complexes, and the results explained the structure-activity relationships observed in vitro, which may provide some useful information for future design of new insecticides.
