Ryanodine receptors（RyRs） activator has become one class of popular insecticide because of its unique mode of action. In order to find more new RyRs activators as insecticidal agents, a series of 18 novel chiral ant...Ryanodine receptors（RyRs） activator has become one class of popular insecticide because of its unique mode of action. In order to find more new RyRs activators as insecticidal agents, a series of 18 novel chiral anthranilic diamides were designed by introducing the D-alanine acid and D-serine acid esters as well as trifluoroethoxyl group into the anthranilic diamide skeleton and synthesized successfully based on anthranilic diamide and FKI-1033 structures. The structures of the title compounds Ia–i and IIa–i were confirmed by melting points,~1H NMR,^（13）C NMR, elemental analysis and specific optical rotation analysis.The preliminary bioassay results indicated that most of the title compounds exhibited considerable larvicidal activities against oriental armyworm at 10 mg/L, especially Ib, Ie and IIh showed remarkable insecticidal activities at 0.5 mg/L. The larvicidal activity against diamondback moth of Ia and IId were 80%and 90% respectively at 0.0001 mg/L, which was similar to that of chlorantraniliprole. The relationship between structure and insecticidal activity was analyzed to reveal a possible co-regulated effect of the chiral amino acid ester, halogen atom or cyano group, and trifluoroethyloxyl group of the skeleton structures of the title compounds, which will provide useful information for guiding the design and discovery of new RyRs activators and insecticidal agrochemicals.展开更多
A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ~...A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ~1H NMR,^（13）C NMR,^（19）F NMR and HRMS.The preliminary bioassays indicated that half of the title compounds were endowed with good insecticidal activities against armyworm（Mythimna sepatara） at the concentration of 500 mg/L,Exhilaratingly,the synthesized compound 3a was also active against Tetranychus cinnabarinus at 100 mg/L.The difference in activities between the target compounds was influenced by the substituents,which provided some hints for further investigation on structure modifications.展开更多
A ring-opening process of 4-imino-1,3-thiazetidin-2-ones with NH2OH.HCI was described for the first time. Two different scaffolds of imidodicarbonic diamide were obtained selectively in good yields in the presence of ...A ring-opening process of 4-imino-1,3-thiazetidin-2-ones with NH2OH.HCI was described for the first time. Two different scaffolds of imidodicarbonic diamide were obtained selectively in good yields in the presence of organic base. The obtained imidodicarbonic diamides were demonstrated by X-ray diffraction analysis.展开更多
The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rar...The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rare earth metal ions and as membrane active compounds in plasticized polymeric membranes of potentiometric sensors.It is found that scandium is extracted with 2,6-pyridinedicarboxylic acid diamides similarly to heavy lanthanides,while yttrium is extracted together with light group lanthanides.DPA shows high selectivity for the separation of cadmium/zinc,lead/nickel or copper/nickel pairs.The four out of six studied ligands demonstrate significant potentiometric sensitivity towards scandium,yttrium and lanthanides in 10^(-7)-10^(-3)mol/L concentration range in nitric acid solutions.The trends in sensitivity values vary depending on a ligand structure and the highest values are observed for Sc^(3+)and heavy lanthanides.According to the evaluated selectivity Sm^(3+)is the most preferred ion,while La^(3+)is the most discriminated.The differences in sensor behavior in rare earth metal solutions assume that such devices can be applied in sensor arrays for potentiometric analysis of lanthanide mixtures.展开更多
In order to search for novel potent and environmentally benign insecticides,a series of anthranilic diamides containing various fluorinated groups were designed and synthesized.Their structures were confirmed by -1H N...In order to search for novel potent and environmentally benign insecticides,a series of anthranilic diamides containing various fluorinated groups were designed and synthesized.Their structures were confirmed by -1H NMR,-（13）C NMR,-（19）F NMR,elemental analysis,HRMS or mass spectra.Their insecticidal activities against oriental armyworm（Mythimna separata） and diamondback moth（Plutella xyiostella）were evaluated.The preliminary structure-activity relationship（SAR） was discussed in detail.The biological assay indicated that most of the compounds exhibited moderate to excellent insecticidal activities.Especially,Ia showed high larvicidal activity against oriental armyworm.Meanwhile,Iu had better larvicidal effects against diamondback moth than commercial chlorantraniliprole.展开更多
To search for potent insecticides targeting at ryanodine receptors(RyRs),a series of novel anthranilic diamides analogs containing 4-chlorine N-pyridylpyrazole were designed and synthesized.Their insecticidal activiti...To search for potent insecticides targeting at ryanodine receptors(RyRs),a series of novel anthranilic diamides analogs containing 4-chlorine N-pyridylpyrazole were designed and synthesized.Their insecticidal activities were evaluated and the preliminary struc ture-activity relationships(SARs)were discussed.The insecticidal results showed that some of the compounds(8a-8h,8m,8n)exhibited good larvicidal activities against oriental armyworm at 2.5 mg·L^(-1),and compound 8m possessed 60%insecticidal activityat 0.5 mg·L^(-1).For diamondback moth,8m exhibited better activity than Chlorantraniliprole at a hundred fold preference.展开更多
Anthranilic diamides have been proven to be a class of efficacious and safe insecticides targeting ryanodine receptors (RyRs) during the last decade. In order to develop innovative scaffolds with high insecticidal act...Anthranilic diamides have been proven to be a class of efficacious and safe insecticides targeting ryanodine receptors (RyRs) during the last decade. In order to develop innovative scaffolds with high insecticidal activity, two series of N-pyridylpyrazole derivatives containing N-(tert-butyl)benzohydrazide substructures were designed and synthesized. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) were evaluated. Preliminary bioassay results revealed that some of the new compounds exhibited good insecticidal activity against the oriental armyworm and diamondback moth. The mode of action of these compounds were verified using calcium-imaging technique and the results showed that some new compounds could effectively modulate the insect cytosolic Ca^2+ level, and break the cellular calcium homeostasis, indicating some of these compounds were potent activators of the RyRs.展开更多
In order to discover novel insecticides with the new action mode on ryanodine receptor （RyR）, a series of novel phthalic acid diamide derivatives were designed and synthesized. All compounds were characterized by 1H...In order to discover novel insecticides with the new action mode on ryanodine receptor （RyR）, a series of novel phthalic acid diamide derivatives were designed and synthesized. All compounds were characterized by 1H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that some title compounds exhibited excellent insecticidal activities against Mythimna separata, Spodoptera exigua, and Plutella xylostella. The title compound 3-nitro-N-cyclopropyl-N＇-[2-methyl-4-（perfluoropropan-2-yl）phenyl]phthalamidte （4a） was more efficient against diamondback moths than the control （chlorantraniliprole）. The effects of some title compounds on intracellular calcium of neurons from the Spodoptera exigua proved that the title compounds were RyR activators.展开更多
A series of novel phthalic diamide derivatives containing 1,2,3-triazole moiety were synthesized using one-pot click chemistry approach and characterized by ^(1)H NMR and HRMS.The insecticidal activity against armywor...A series of novel phthalic diamide derivatives containing 1,2,3-triazole moiety were synthesized using one-pot click chemistry approach and characterized by ^(1)H NMR and HRMS.The insecticidal activity against armyworm(Mythimna separata),Tetranychus cinnabarinus and cowpea aphid(Aphis craccivora)was evaluated.Compounds 4Ⅱ-a and 4Ⅱ-i showed 50%insecticidal activity against armyworm(Mythimna separata)at the concentration of 4 mg/L and one-third of the compounds had moderate activity against Tetranychus cinnabarinus at 500 mg/L.展开更多
The Bemisia tabaci （Gennadius） cryptic species complex comprises important insect pests that cause devastating damage to agricultural crops worldwide. In China, the B. tabaci Mediterranean （MED） （or biotype Q） s...The Bemisia tabaci （Gennadius） cryptic species complex comprises important insect pests that cause devastating damage to agricultural crops worldwide. In China, the B. tabaci Mediterranean （MED） （or biotype Q） species is threatening agricul- tural production all over the country as resistance to commonly used insecticides has increased. This situation highlights the need for alternative pest control measures. Cyantraniliprole, a novel anthraniiic diamide insecticide, has been widely employed to control Hemipteran pests. To monitor the levels of resistance to cyantraniliprole in B. tabaci field populations in China, bioassays were conducted for 18 field samples from nine provinces over two years. Compared with median lethal concentration （LC^0） for the MED susceptible strain, all field samples had significantly higher resistance to cyantraniliprole. Furthermore, resistance factors （RFs） increased significantly in samples from Shanxi （from 5.62 in 2015 to 25.81 in 2016）, Hunan （3.30 in 2015 to 20.97 in 2016） and Hubei （from 9.81 in 2015 to 23.91 in 2016） provinces. This study indicates a considerable decrease in the efficacy of cyantraniliprole against B. tabaci and establishes a baseline of susceptibility that could serve as a reference for future monitoring and management of B. tabaci resistance to cyantraniliprole.展开更多
Anthranilic diamides are fasting growing class insecticides in modern crop protection for their high activity, low ecotoxicity, and broad insecticidal spectra. However. the bioactive conformations of anthranilic diami...Anthranilic diamides are fasting growing class insecticides in modern crop protection for their high activity, low ecotoxicity, and broad insecticidal spectra. However. the bioactive conformations of anthranilic diamides are still unclear until now. In the present study, DFT-based potential energy surface scanning was used to detect the low energy conformations of chlorantraniliprole, then were used respectively in the structure alignment for a series of anthranilic diamide compounds followed by detailed CoMFA and CoMSIA analyses. Finally, the bioactive conformations of anthranilic diamide insecticides were revealed from a series of low energy conformations, which might provide some clues for future insecticide design.展开更多
Given the development of insects’resistance and deteriorative ecological environment,the discovery of insecticides with a new mode of action has been proven to be an important tool for comprehensive pest management.H...Given the development of insects’resistance and deteriorative ecological environment,the discovery of insecticides with a new mode of action has been proven to be an important tool for comprehensive pest management.Herein,a novel anthranilic diamides containing 3,5-dichloropyridylpyrazole group were designed and synthesized.Their insecticidal potency was assayed against beet armyworm(Spodoptera exigua).Moreover,the structure-activity relationship of these new compounds was also discussed.Of them,compound 15g exhibited potential insecticidal activity.Because of the excellent efficacy against a series of Lepidoptera and low toxicity to mammals,compound 15g,namely tetrachlorantraniliprole,has been developed and launched into the market as an insecticide.展开更多
To study the pesticide effect, action mode, structure-activity relationships (SARs) of anthranilic diamide insecticide and screen highly active pesticides, novel anthranilic diamide derivatives were synthesized.Bioass...To study the pesticide effect, action mode, structure-activity relationships (SARs) of anthranilic diamide insecticide and screen highly active pesticides, novel anthranilic diamide derivatives were synthesized.Bioassays indicated that all of the title compounds displayed 100% mortality against diamondback moth and oriental armyworm at 100 mg/L, among which 12 v and 12 w showed 100% insecticidal acitvity at 5 mg/L. Surprisingly compound 12 w exhibited better insecticidal acitvity than commercialized chlorantraniliprole against Pyrausta nubilalis (0.1 mg/L) and Cnaphalocrocis Medinalis (2 mg/L). 3 D-QSAR and SARs statistical analysis revealed that title compounds with R^2 fixed as methoxy had the highest probability possessing high activity. The calcium fluorescence measurements on neurons revealed that E series compounds containing pyrazinyl may have a molecular target different from caffeine on ryanodine receptors rather than the voltage-gated calcium channel present on cytomembran.展开更多
The effects of three types of electrically-inert fillers, calcium carbonate （CaCO_3）, talc and glass fiber （GF）, on electrical resistivity, crystallization behavior and dynamic mechanical properties of poly（m-xyl...The effects of three types of electrically-inert fillers, calcium carbonate （CaCO_3）, talc and glass fiber （GF）, on electrical resistivity, crystallization behavior and dynamic mechanical properties of poly（m-xylene adipamide） （MXD6）/multiwalled carbon nanotube （MWCNT） composites are investigated. The electrical resistivity of MXD6/MWCNT composites is significantly reduced with the addition of inert fillers due to the volume-exclusion effect that leads to increased effective concentration of MWCNTs in MXD6 matrix and also due to improved MWCNT dispersion. The crystallization temperature of MXD6 increases with the addition of MWCNTs, indicating that MWCNTs can act as nucleating agent and induce crystallization of MXD6. The incorporation of inert fillers has no further effect on crystallization behavior of MXD6, but significantly improves the storage modulus of MXD6/MWCNT composite, demonstrating that CaCO_3, talc and GF filled MXD6/MWCNT composites are very promising materials with not only improved electrical property but also excellent mechanical properties.展开更多
Diamide derivatives are biologically active molecules that have been widely applied in recent years in research on pesticides,especially insecticides.Using a simple and environmentally friendly scheme,a series of new ...Diamide derivatives are biologically active molecules that have been widely applied in recent years in research on pesticides,especially insecticides.Using a simple and environmentally friendly scheme,a series of new diamide derivatives containing a trifluoromethylpyridine skeleton was designed,synthesized,and confirmed by^(1)H,^(19)F and^(13)C NMR,and HR-MS.Their insecticidal activities against Plutella xylostella and Helicoverpa armigera were measured and the relationship between structure and activity was investigated.Eight of the title compounds(D2,D5,D10,D21,D28,D29,D30 and D33)showed 100%activity against P.xylostella at 500 mg L^(-1).One compound,D33,still showed 100%activity against P.xylostella at 100 mg L^(-1)and had the lowest LC_(50)(lethal concentration 50%,3.7 mg L^(-1))among the synthesized compounds.Molecular docking analysis revealed that D33 could be thoroughly embedded in the active pocket of the ryanodine receptor via hydrogen bonding in a manner similar to the commercial insecticide chlorantraniliprole.展开更多
Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the f...Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.展开更多
Thirteen novel phenyl substituted isoxazolecarboxamides were synthesized, and their structures were characterized by IH NMR, elementary analysis and high-resolution mass spectrometry（HRMS） techniques. Their evaluate...Thirteen novel phenyl substituted isoxazolecarboxamides were synthesized, and their structures were characterized by IH NMR, elementary analysis and high-resolution mass spectrometry（HRMS） techniques. Their evaluated insecticidal activities against oriental armyworm（Mythimna separata） indicate that the phenyl substituted isoxazolecarboxamides exhibited moderate insecticidal activities, among which compounds 9c and 9k showed com- paratively higher activities.展开更多
Twelve novel analogues of chlorantraniliprole containing nitro group were synthesized,and their structures were characterized by 1H NMR and high-resolution mass spectrometry（HRMS）.Their evaluated insecticidal activi...Twelve novel analogues of chlorantraniliprole containing nitro group were synthesized,and their structures were characterized by 1H NMR and high-resolution mass spectrometry（HRMS）.Their evaluated insecticidal activities against oriental armyworm（Mythimna separata） indicate that the nitro-containing analogues showed favorable insecticidal activities,while the activity of compounds 5g at 0.25mg/L was 40%,but still lower than chlorantraniliprole.展开更多
Diamides acting on insect ryanodine receptors are an intensive research area now. In order to search for novel candidates, a series of diamides containing biphenyl substructure were designed and synthesized.Their inse...Diamides acting on insect ryanodine receptors are an intensive research area now. In order to search for novel candidates, a series of diamides containing biphenyl substructure were designed and synthesized.Their insecticidal activities against armyworms（Mythimna sepatara） and aphis（Aphis craccivora） were screened. The compounds with 3,5-dichloro-4-（1,1,2,2-tetrafluoroethoxy）phenyl substituent were found to be insecticidal to armyworms with the similar symptoms to poisoning by flubendiamide. In this research, we presented a novel type of diamide insecticide as a lead compound for further optimization.展开更多
In order to study whether the endothelial cells (ECs) with lipid peroxidation induced by diamide can express and secrete macrophage inflammatory protein 1α (MIP-1α), the expression of MIP-1α protein in the cells wa...In order to study whether the endothelial cells (ECs) with lipid peroxidation induced by diamide can express and secrete macrophage inflammatory protein 1α (MIP-1α), the expression of MIP-1α protein in the cells was detected by cell enzyme-linked immunosorbent assay (ELISA) and that of MIP-1α mRNA was determined by cell in situ hybridization and nuclease S1 protection assay after the ECs were exposed to different concentrations of diamide for 4 h. The chemotactic activity of MIP-1α was tested by micropore filter method using modified Boyden chambers. Cell ELISA showed that the expression of MIP-1α protein in endothelial cells exposed to 1 μmol/L, 5 μmol/L and 10 μmol/L diamide was 1.9-fold, 2.3-fold and 1.7-fold respectively as much as that in the control cells, which was statistically significant by analysis of variance. In situ hybridization revealed that the mRNA expression of ECs treated with 1 μmol/L, 5 μmol/L and 10 μmol/L diamide was 1 3-fold, 3.0-fold and 1.7-fold as much as that in the control group, which had statistical significance ( F =188.93, P <0.01). The mRNA expression in 5 μmol/L dimide treated ECs, measured by nuclease S1 protection assay, was 3.4-fold as much as that in the control group( t =8 70, P <0 05). Chemotactic response(99.50±4.31 μm) to the culture medium conditioned by 5 μmol/L diamide treated ECs , which was stronger than that(66.47±3.25 μm) conditioned by the ECs ( F =404.31, P <0.05), was significantly decreased ( F =192.25, P <0.05) after adding MIP-1α antibody. It suggests that diamide, a lipid peroxidation inducer, could stimulate ECs to produce high level of MIP-1α, and might play an important role in atherogenesis by promoting the migration of peripheral blood monocytes into arterial intima.展开更多
基金supported by the National Natural Science Foundation of China(Nos. 21772103, 21602118)the National Key Research and Development Program of China (No. 2017YFD0200505)Tianjin Natural Science Foundation (No. 17JCYBJC19900)
文摘Ryanodine receptors（RyRs） activator has become one class of popular insecticide because of its unique mode of action. In order to find more new RyRs activators as insecticidal agents, a series of 18 novel chiral anthranilic diamides were designed by introducing the D-alanine acid and D-serine acid esters as well as trifluoroethoxyl group into the anthranilic diamide skeleton and synthesized successfully based on anthranilic diamide and FKI-1033 structures. The structures of the title compounds Ia–i and IIa–i were confirmed by melting points,~1H NMR,^（13）C NMR, elemental analysis and specific optical rotation analysis.The preliminary bioassay results indicated that most of the title compounds exhibited considerable larvicidal activities against oriental armyworm at 10 mg/L, especially Ib, Ie and IIh showed remarkable insecticidal activities at 0.5 mg/L. The larvicidal activity against diamondback moth of Ia and IId were 80%and 90% respectively at 0.0001 mg/L, which was similar to that of chlorantraniliprole. The relationship between structure and insecticidal activity was analyzed to reveal a possible co-regulated effect of the chiral amino acid ester, halogen atom or cyano group, and trifluoroethyloxyl group of the skeleton structures of the title compounds, which will provide useful information for guiding the design and discovery of new RyRs activators and insecticidal agrochemicals.
基金supported by National Basic Research Program of China(973 Program,No.2010CB126100)National High Technology Research and Development Program of China (863 Program,No.2011AA10A207)supported by National Key Technology R&D Program of China(No. 2011BAE06B01)
文摘A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ~1H NMR,^（13）C NMR,^（19）F NMR and HRMS.The preliminary bioassays indicated that half of the title compounds were endowed with good insecticidal activities against armyworm（Mythimna sepatara） at the concentration of 500 mg/L,Exhilaratingly,the synthesized compound 3a was also active against Tetranychus cinnabarinus at 100 mg/L.The difference in activities between the target compounds was influenced by the substituents,which provided some hints for further investigation on structure modifications.
基金the Natural Science Foundation of Zhejiang Province(No.LY13B020015)the Science and Technology Plan Project of Taizhou(No.131KY03)for financial support
文摘A ring-opening process of 4-imino-1,3-thiazetidin-2-ones with NH2OH.HCI was described for the first time. Two different scaffolds of imidodicarbonic diamide were obtained selectively in good yields in the presence of organic base. The obtained imidodicarbonic diamides were demonstrated by X-ray diffraction analysis.
文摘The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rare earth metal ions and as membrane active compounds in plasticized polymeric membranes of potentiometric sensors.It is found that scandium is extracted with 2,6-pyridinedicarboxylic acid diamides similarly to heavy lanthanides,while yttrium is extracted together with light group lanthanides.DPA shows high selectivity for the separation of cadmium/zinc,lead/nickel or copper/nickel pairs.The four out of six studied ligands demonstrate significant potentiometric sensitivity towards scandium,yttrium and lanthanides in 10^(-7)-10^(-3)mol/L concentration range in nitric acid solutions.The trends in sensitivity values vary depending on a ligand structure and the highest values are observed for Sc^(3+)and heavy lanthanides.According to the evaluated selectivity Sm^(3+)is the most preferred ion,while La^(3+)is the most discriminated.The differences in sensor behavior in rare earth metal solutions assume that such devices can be applied in sensor arrays for potentiometric analysis of lanthanide mixtures.
基金financially supported by the National Natural Science Foundation of China(No.21372133)973 Program(No.2010CB126106)"111" Project of Ministry of Education of China(No.B06005)
文摘In order to search for novel potent and environmentally benign insecticides,a series of anthranilic diamides containing various fluorinated groups were designed and synthesized.Their structures were confirmed by -1H NMR,-（13）C NMR,-（19）F NMR,elemental analysis,HRMS or mass spectra.Their insecticidal activities against oriental armyworm（Mythimna separata） and diamondback moth（Plutella xyiostella）were evaluated.The preliminary structure-activity relationship（SAR） was discussed in detail.The biological assay indicated that most of the compounds exhibited moderate to excellent insecticidal activities.Especially,Ia showed high larvicidal activity against oriental armyworm.Meanwhile,Iu had better larvicidal effects against diamondback moth than commercial chlorantraniliprole.
基金The project was supported by the National Key Research Program-The Innovation of Eco-Modulator of Insect Ryanodine Re-ceptor(Nos.2018YFD0200100,2017YFD0200505)the National Natural Science Foundation of China(Nos.31972287,21602118).
文摘To search for potent insecticides targeting at ryanodine receptors(RyRs),a series of novel anthranilic diamides analogs containing 4-chlorine N-pyridylpyrazole were designed and synthesized.Their insecticidal activities were evaluated and the preliminary struc ture-activity relationships(SARs)were discussed.The insecticidal results showed that some of the compounds(8a-8h,8m,8n)exhibited good larvicidal activities against oriental armyworm at 2.5 mg·L^(-1),and compound 8m possessed 60%insecticidal activityat 0.5 mg·L^(-1).For diamondback moth,8m exhibited better activity than Chlorantraniliprole at a hundred fold preference.
基金the NSFC/China (No.21502229)Tianjin Natural Science Foundation (No.16JCYBJC29400).
文摘Anthranilic diamides have been proven to be a class of efficacious and safe insecticides targeting ryanodine receptors (RyRs) during the last decade. In order to develop innovative scaffolds with high insecticidal activity, two series of N-pyridylpyrazole derivatives containing N-(tert-butyl)benzohydrazide substructures were designed and synthesized. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) were evaluated. Preliminary bioassay results revealed that some of the new compounds exhibited good insecticidal activity against the oriental armyworm and diamondback moth. The mode of action of these compounds were verified using calcium-imaging technique and the results showed that some new compounds could effectively modulate the insect cytosolic Ca^2+ level, and break the cellular calcium homeostasis, indicating some of these compounds were potent activators of the RyRs.
基金Supporting information for this article is available on the WWW under http：//dx.doi.org/10.1002/cjoc.2011 00745 or from the author.Acknowledgement This work was supported by the National Natural Science Foundation of China （No. 20872069）, National Basic Research Program of China （No. 2010CB126106）, the National Key Technologies R＆D Program （No. 2011BAE06B05） and Tianjin Natural Science Foundation （No. 11JCYBJC08600）
文摘In order to discover novel insecticides with the new action mode on ryanodine receptor （RyR）, a series of novel phthalic acid diamide derivatives were designed and synthesized. All compounds were characterized by 1H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that some title compounds exhibited excellent insecticidal activities against Mythimna separata, Spodoptera exigua, and Plutella xylostella. The title compound 3-nitro-N-cyclopropyl-N＇-[2-methyl-4-（perfluoropropan-2-yl）phenyl]phthalamidte （4a） was more efficient against diamondback moths than the control （chlorantraniliprole）. The effects of some title compounds on intracellular calcium of neurons from the Spodoptera exigua proved that the title compounds were RyR activators.
基金This work was financially supported by the National Basic Research Program of China(973 Program,No.2010CB126100)the National High Technology Research and Development Program of China(863 Program Program,No.2011AA10A207)+2 种基金the National Natural Science Foundation of China(Nos.2137207921272071)This work was also partly supported by the National Key Technology R&D Program of China(No.2011BAE06B01)and the Fundamental Research Funds for the Central Universities.
文摘A series of novel phthalic diamide derivatives containing 1,2,3-triazole moiety were synthesized using one-pot click chemistry approach and characterized by ^(1)H NMR and HRMS.The insecticidal activity against armyworm(Mythimna separata),Tetranychus cinnabarinus and cowpea aphid(Aphis craccivora)was evaluated.Compounds 4Ⅱ-a and 4Ⅱ-i showed 50%insecticidal activity against armyworm(Mythimna separata)at the concentration of 4 mg/L and one-third of the compounds had moderate activity against Tetranychus cinnabarinus at 500 mg/L.
基金supported by the National Natural Science Foundation of China (31601635)the Beijing Natural Science Foundation,China (6174038)the earmarked fund for Beijing Innovation Consortium of Agriculture Research System,China (BAIC07-2017)
文摘The Bemisia tabaci （Gennadius） cryptic species complex comprises important insect pests that cause devastating damage to agricultural crops worldwide. In China, the B. tabaci Mediterranean （MED） （or biotype Q） species is threatening agricul- tural production all over the country as resistance to commonly used insecticides has increased. This situation highlights the need for alternative pest control measures. Cyantraniliprole, a novel anthraniiic diamide insecticide, has been widely employed to control Hemipteran pests. To monitor the levels of resistance to cyantraniliprole in B. tabaci field populations in China, bioassays were conducted for 18 field samples from nine provinces over two years. Compared with median lethal concentration （LC^0） for the MED susceptible strain, all field samples had significantly higher resistance to cyantraniliprole. Furthermore, resistance factors （RFs） increased significantly in samples from Shanxi （from 5.62 in 2015 to 25.81 in 2016）, Hunan （3.30 in 2015 to 20.97 in 2016） and Hubei （from 9.81 in 2015 to 23.91 in 2016） provinces. This study indicates a considerable decrease in the efficacy of cyantraniliprole against B. tabaci and establishes a baseline of susceptibility that could serve as a reference for future monitoring and management of B. tabaci resistance to cyantraniliprole.
基金the financial support from the National Key Technology R&D Program of China (No.2011BAE06B05)
文摘Anthranilic diamides are fasting growing class insecticides in modern crop protection for their high activity, low ecotoxicity, and broad insecticidal spectra. However. the bioactive conformations of anthranilic diamides are still unclear until now. In the present study, DFT-based potential energy surface scanning was used to detect the low energy conformations of chlorantraniliprole, then were used respectively in the structure alignment for a series of anthranilic diamide compounds followed by detailed CoMFA and CoMSIA analyses. Finally, the bioactive conformations of anthranilic diamide insecticides were revealed from a series of low energy conformations, which might provide some clues for future insecticide design.
基金supported by the National Key Research&Development Pillar Program of China during the 13th Five-Year Plan Period(Grant No.2016YFD0300708,2016YFD0300709).
文摘Given the development of insects’resistance and deteriorative ecological environment,the discovery of insecticides with a new mode of action has been proven to be an important tool for comprehensive pest management.Herein,a novel anthranilic diamides containing 3,5-dichloropyridylpyrazole group were designed and synthesized.Their insecticidal potency was assayed against beet armyworm(Spodoptera exigua).Moreover,the structure-activity relationship of these new compounds was also discussed.Of them,compound 15g exhibited potential insecticidal activity.Because of the excellent efficacy against a series of Lepidoptera and low toxicity to mammals,compound 15g,namely tetrachlorantraniliprole,has been developed and launched into the market as an insecticide.
基金supported by the National Natural Science Foundation of China(Nos. 20772060 and 21172114)
文摘To study the pesticide effect, action mode, structure-activity relationships (SARs) of anthranilic diamide insecticide and screen highly active pesticides, novel anthranilic diamide derivatives were synthesized.Bioassays indicated that all of the title compounds displayed 100% mortality against diamondback moth and oriental armyworm at 100 mg/L, among which 12 v and 12 w showed 100% insecticidal acitvity at 5 mg/L. Surprisingly compound 12 w exhibited better insecticidal acitvity than commercialized chlorantraniliprole against Pyrausta nubilalis (0.1 mg/L) and Cnaphalocrocis Medinalis (2 mg/L). 3 D-QSAR and SARs statistical analysis revealed that title compounds with R^2 fixed as methoxy had the highest probability possessing high activity. The calcium fluorescence measurements on neurons revealed that E series compounds containing pyrazinyl may have a molecular target different from caffeine on ryanodine receptors rather than the voltage-gated calcium channel present on cytomembran.
文摘The effects of three types of electrically-inert fillers, calcium carbonate （CaCO_3）, talc and glass fiber （GF）, on electrical resistivity, crystallization behavior and dynamic mechanical properties of poly（m-xylene adipamide） （MXD6）/multiwalled carbon nanotube （MWCNT） composites are investigated. The electrical resistivity of MXD6/MWCNT composites is significantly reduced with the addition of inert fillers due to the volume-exclusion effect that leads to increased effective concentration of MWCNTs in MXD6 matrix and also due to improved MWCNT dispersion. The crystallization temperature of MXD6 increases with the addition of MWCNTs, indicating that MWCNTs can act as nucleating agent and induce crystallization of MXD6. The incorporation of inert fillers has no further effect on crystallization behavior of MXD6, but significantly improves the storage modulus of MXD6/MWCNT composite, demonstrating that CaCO_3, talc and GF filled MXD6/MWCNT composites are very promising materials with not only improved electrical property but also excellent mechanical properties.
基金supported by the National Natural Science Foundation of China (21762012, 32072445 and 21562012)the Program of Introducing Talents to Chinese Universities (D20023)the S&T Planning Project of Guizhou Province, China ([2017]1402 and [2017]5788)
文摘Diamide derivatives are biologically active molecules that have been widely applied in recent years in research on pesticides,especially insecticides.Using a simple and environmentally friendly scheme,a series of new diamide derivatives containing a trifluoromethylpyridine skeleton was designed,synthesized,and confirmed by^(1)H,^(19)F and^(13)C NMR,and HR-MS.Their insecticidal activities against Plutella xylostella and Helicoverpa armigera were measured and the relationship between structure and activity was investigated.Eight of the title compounds(D2,D5,D10,D21,D28,D29,D30 and D33)showed 100%activity against P.xylostella at 500 mg L^(-1).One compound,D33,still showed 100%activity against P.xylostella at 100 mg L^(-1)and had the lowest LC_(50)(lethal concentration 50%,3.7 mg L^(-1))among the synthesized compounds.Molecular docking analysis revealed that D33 could be thoroughly embedded in the active pocket of the ryanodine receptor via hydrogen bonding in a manner similar to the commercial insecticide chlorantraniliprole.
基金supported by the National Natural Science Foundation of China(Nos.U1967216,22076188,U20B2019,21876174)the National Science Fund for Distinguished Young Scholars(No.21925603).
文摘Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.
基金Supported by the National Natural Science Foundation of China(No. 20872069)the National Basic Research Program of China(No.2010CB126106)the Fund of State Key Laboratory of Elemento-Organic Chemistry,China
文摘Thirteen novel phenyl substituted isoxazolecarboxamides were synthesized, and their structures were characterized by IH NMR, elementary analysis and high-resolution mass spectrometry（HRMS） techniques. Their evaluated insecticidal activities against oriental armyworm（Mythimna separata） indicate that the phenyl substituted isoxazolecarboxamides exhibited moderate insecticidal activities, among which compounds 9c and 9k showed com- paratively higher activities.
基金Supported by the National Basic Research Program of China(No.2010CB126106)
文摘Twelve novel analogues of chlorantraniliprole containing nitro group were synthesized,and their structures were characterized by 1H NMR and high-resolution mass spectrometry（HRMS）.Their evaluated insecticidal activities against oriental armyworm（Mythimna separata） indicate that the nitro-containing analogues showed favorable insecticidal activities,while the activity of compounds 5g at 0.25mg/L was 40%,but still lower than chlorantraniliprole.
文摘Diamides acting on insect ryanodine receptors are an intensive research area now. In order to search for novel candidates, a series of diamides containing biphenyl substructure were designed and synthesized.Their insecticidal activities against armyworms（Mythimna sepatara） and aphis（Aphis craccivora） were screened. The compounds with 3,5-dichloro-4-（1,1,2,2-tetrafluoroethoxy）phenyl substituent were found to be insecticidal to armyworms with the similar symptoms to poisoning by flubendiamide. In this research, we presented a novel type of diamide insecticide as a lead compound for further optimization.
文摘In order to study whether the endothelial cells (ECs) with lipid peroxidation induced by diamide can express and secrete macrophage inflammatory protein 1α (MIP-1α), the expression of MIP-1α protein in the cells was detected by cell enzyme-linked immunosorbent assay (ELISA) and that of MIP-1α mRNA was determined by cell in situ hybridization and nuclease S1 protection assay after the ECs were exposed to different concentrations of diamide for 4 h. The chemotactic activity of MIP-1α was tested by micropore filter method using modified Boyden chambers. Cell ELISA showed that the expression of MIP-1α protein in endothelial cells exposed to 1 μmol/L, 5 μmol/L and 10 μmol/L diamide was 1.9-fold, 2.3-fold and 1.7-fold respectively as much as that in the control cells, which was statistically significant by analysis of variance. In situ hybridization revealed that the mRNA expression of ECs treated with 1 μmol/L, 5 μmol/L and 10 μmol/L diamide was 1 3-fold, 3.0-fold and 1.7-fold as much as that in the control group, which had statistical significance ( F =188.93, P <0.01). The mRNA expression in 5 μmol/L dimide treated ECs, measured by nuclease S1 protection assay, was 3.4-fold as much as that in the control group( t =8 70, P <0 05). Chemotactic response(99.50±4.31 μm) to the culture medium conditioned by 5 μmol/L diamide treated ECs , which was stronger than that(66.47±3.25 μm) conditioned by the ECs ( F =404.31, P <0.05), was significantly decreased ( F =192.25, P <0.05) after adding MIP-1α antibody. It suggests that diamide, a lipid peroxidation inducer, could stimulate ECs to produce high level of MIP-1α, and might play an important role in atherogenesis by promoting the migration of peripheral blood monocytes into arterial intima.
