At present,developing high-efficiency microwave absorption materials with properties including lightweight,thin thickness,strong absorbing intensity and broad bandwidth is an urgent demand to solve the electromagnetic...At present,developing high-efficiency microwave absorption materials with properties including lightweight,thin thickness,strong absorbing intensity and broad bandwidth is an urgent demand to solve the electromagnetic pollution issues.An ideal microwave absorber should have excellent dielectric and magnetic loss capabilities,thereby inducing attenuation and absorption of incident electromagnetic radiation.Recently,various carbon/magnetic metal composites have been developed and expected to become promising candidates for high-performance microwave absorbers.In this review,we introduce the mechanisms of microwave absorption and summarize the recent advances in carbon/magnetic metal composites.Preparation methods and microwave absorption properties of carbon/magnetic metal composites with different components,morphologies and microstructures are discussed in detail.Finally,the challenges and future prospects of carbon/magnetic metal absorbing materials are also proposed,which will be useful to develop high-performance microwave absorption materials.展开更多
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 1,2,4-oxadiazole-containing N-pyridylpyrazole derivatives 12 a-h were efficiently synthesized with pivaldehyde,pyridylpyrazole carboxylic acid and arylamine as raw materials via 1,3-dipolar cycloaddi...A series of novel 1,2,4-oxadiazole-containing N-pyridylpyrazole derivatives 12 a-h were efficiently synthesized with pivaldehyde,pyridylpyrazole carboxylic acid and arylamine as raw materials via 1,3-dipolar cycloaddition.Their structures were identified by melting points,1 H NMR,13 C NMR and elemental analysis or HRMS.The exploration on the single-crystal structures of 12 c and 12 g revealed the stereochemical and substituent oriental characteristics,and the relevance of the structure and the reaction activity of this type of compounds.The preliminary bioassays indicated that several compounds had good insecticidal activities,among which 12 c showed a lethality rate of 80%towards Mythimna separata Walker at 200μg/mL;some of the compounds exhibited favorable fungicidal activities at 50μg/mL against Physalospora piricola,Rhizoctonia cereal,Sclerotinia sclerotiorum,etc.Among which,12 a,12 b,12 c and 12 h could be considered as new fungicidal leading compounds for further structural optimization.These discoveries along with the structure-activity relationship analysis in this paper will provide useful guidance for the innovative studies on new pyridylpyrazole derivatives and their applications in agrochemical area.展开更多
The study of soil degradation behaviors of sulfonylurea herbicides in relation to their different structural attributes is utmost important for us to comprehend the development of new eco-friendly herbicides. It is po...The study of soil degradation behaviors of sulfonylurea herbicides in relation to their different structural attributes is utmost important for us to comprehend the development of new eco-friendly herbicides. It is postulated that the structural modification of the chemical structures could influence their degradation rates in soil. Nine devised structures were synthesized to study their herbicidal activity as well as their soil degradation behaviors respectively. The novel compounds I-3-I-7 were characterized by UV, ^1H NMR and ^13C NMR, MS and EA. Bioassays indicated that most of target compounds displayed superior herbicidal activities in comparison with Chlorsulfuron. Soil degradation results further confirmed our previous assumption that the introduction of electron-donating substituents at 54 position of the benzene ring distinctly increased their degradation rates, among which dimethylamino and diethylamino groups can adjust the degradation rate to a more favorable status.展开更多
A series of novel furan/thiophene and piperazine-containing 1,2,4-triazole Mannich bases and bis(1,2,4-triazole) Mannich bases have been conveniently synthesized via Mannich reaction with triazole Schiff bases, vari...A series of novel furan/thiophene and piperazine-containing 1,2,4-triazole Mannich bases and bis(1,2,4-triazole) Mannich bases have been conveniently synthesized via Mannich reaction with triazole Schiff bases, various pipera- zinc derivatives, and formaldehyde as intermediates in good yields. Their structures were characterized by melting points, ~H NMR, 13C NMR, IR and elemental analysis. The preliminary bioassay showed that most compounds ex- hibited significant in vitro and in vivo fungicidal activity against several test plant fungi. Among 32 new compounds, the trifluoromethyl-containing compounds showed superior activity than the methyl-containing ones. Several com- pounds, such as FS, F9, F10, G5, HT, 118, 13 and 14, were comparable with some commercial fungicides against different fungi during the present study and could be further structurally optimized. Meanwhile, several compounds showed good herbicidal activity against Brassica campestris at 100 ~tg/mL and KARl inhibitory activity at 200 μg/mL. However, compounds exhibited poor insecticidal activity against oriental armyworm at 200 μg/mL in the preliminary studies. The research results will provide useful information for the design and discovery of new agro- chemicals with novel heterocyclic structures.展开更多
Two series of N-pyridylpyrazolecarboxamide derivatives were designed and synthesized by introducing D-alanine acid esters and D-serine acid esters into the skelecton of chlorantraniliprole. The obtained structures wer...Two series of N-pyridylpyrazolecarboxamide derivatives were designed and synthesized by introducing D-alanine acid esters and D-serine acid esters into the skelecton of chlorantraniliprole. The obtained structures were characterized by 1H NMR, 13C NMR, elemental analysis and specific optical rotation analysis. Preliminary bioas-says indicated that some compounds displayed excellent insecticidal activities against Mythimna separate and Plutella xylostella in comparison with chlorantraniliprole. In particular, IIq showed excellent insecticidal activity against Plutella xylostella with a mortality rate of 90% at 0.01 mg·L^-1. A 3D-QSAR (CoMSIA) study was per- formed in order to disclose the insecticidal structure-activity relationship and indicate the future work. The CoMS1A study demonstrated that large substitutes and electron deficient groups at the 3-position of pyrazole ring are favora- ble, the same as a small group near the ester groups of amino acid.展开更多
A series of novel phenylpyrazole carboxylic acid derivatives containing fluorine moiety,i.e.,diamides 11,simple aryl-bearing amides 12 and acylthioureas 14 were successfully synthesized based on the key fluo ro-contai...A series of novel phenylpyrazole carboxylic acid derivatives containing fluorine moiety,i.e.,diamides 11,simple aryl-bearing amides 12 and acylthioureas 14 were successfully synthesized based on the key fluo ro-containing phe nylpyrazole acid intermediate.The new compounds were identified and confirmed by melting point,1H NMR,13C NMR and elemental analysis or HRMS.The bioassay results indicated that some of the compounds possessed excellent insecticidal activities towards oriental armyworm,diamondback moth and corn borer at low concentrations.For examples,compounds 11a,11e-g and 14b exhibited remarkable larvicidal activities with LC50 values of 0.13-0.39 mg/L and 0.0002-0.0014 mg/L against oriental armyworm and diamondback moth,respectively,were comparable with those of the control chlorantraniliprole.Particularly,lie were found superior to chlorantraniliprole in oriental armyworm tests(LC50:0.23 mg/L vs.0.26 mg/L);11a,lie,11f and 14c in diamondback moth tests with LC50 values of 0.0002 mg/L,0.0002 mg/L,0.0008 mg/L and 0.0005 mg/L,respectively,we re more effective than that of chlorantraniliprole.In addition,12 a also showed a promising insecticidal potential and development/optimization advantage.Compounds 11a,lle-g,12a,14b and 14c could be considered as possible new leading structures for further study.The SAR investigation indicated that the compounds with fluorine motif(e.g.,-F,-CF2H,-CF3)held apparently favorable insecticidal potentials,which provided useful guidance for further design/development of new phenylpyrazole-containing agrochemicals.展开更多
With the aim of discovering new bioactive pesticides for crop protection,a series of novel sulfidecontaining amide derivatives A were efficiently synthesized via a strategy of modifying the“amide”structure of anthra...With the aim of discovering new bioactive pesticides for crop protection,a series of novel sulfidecontaining amide derivatives A were efficiently synthesized via a strategy of modifying the“amide”structure of anthranilic diamide insecticides.The single-crystal structures of A2-3 and A4-5 were firstly reported.The bioassay results showed that most of the synthesized compounds display moderate to high insecticidal activities.Particularly,some sulfone-containing compounds,e.g.,A2-3,A3-3 and A6-3,not only possessed favorable lethality rate(50%–100%)against P.xylostella at a concentration of 0.1 mg/L,but also held good activities towards a variety of agricultural pests such as M.separata,C.pipiens pallen,H.armigera and O.nubilalis;the larvicidal activities of A4-1 and A6-1 towards P.xylostella were close to that of chlorantraniliprole at 0.01 mg/L.The calcium imaging experiments revealed that the representative compounds A2-3 and A6-3 are potential ryanodine receptor(RyR)modulators.The structure–activity relationships were discussed in detail.These results provide useful information for further design and development of novel insecticides.展开更多
Diamide compounds such as chlorantraniliprole,a famous anthranilic diamide insecticide targeting the insect ryanodine receptor(Ry R),have received continuous attention in pesticide research during the past 15 years ow...Diamide compounds such as chlorantraniliprole,a famous anthranilic diamide insecticide targeting the insect ryanodine receptor(Ry R),have received continuous attention in pesticide research during the past 15 years owing to their excellent insecticidal potentials.With the aim of discovering new heterocyclic pesticides used for crop protection,based on the structural information of compound M from the reported pharmacophore-based virtual screening for Ry R insecticides and diamide compound,a series of new heterocyclic mono-,di-,and tri-amide derivatives containing piperazine moiety have been synthesized in this paper.The new compounds were identified and confirmed by melting point,^(1)H NMR,^(13)C NMR and HRMS.Compound M was firstly validated for insecticidal activities,and the new synthesized compounds were all made comprehensive insecticidal evaluations against diamondback moth and oriental armyworm.The bioassay results showed that some of the compounds exhibit favorable insecticidal potentials,particularly some novel piperazine-containing heterocyclic mono-/di-/tri-amide derivatives such as 8 g,14 a,15 a,15 g,15 i,15 j,15 k,15 l,and 15 m could be used as new insecticidal leading structures for further study(e.g.,towards diamondback moth,15i-15 m LC_(50):0.0022-0.0081 mg/L).The structure-activity relationships of the compounds discussed in detail provide useful guidance for further design and development of new insecticides.展开更多
Due to a novel mode action,low toxicity to mammals and low residue characteristics,phthalic acid diamides have aroused considerable interests in agricultural chemistry.With introduction of N-cyano,N-trifluoroacetyl,N-...Due to a novel mode action,low toxicity to mammals and low residue characteristics,phthalic acid diamides have aroused considerable interests in agricultural chemistry.With introduction of N-cyano,N-trifluoroacetyl,N-carbamoylsulfiliminyl and sulfoximinyl substituents into phthalamides,12 novel derivatives containing trifluoromethyl moiety were designed and synthesized.All title compounds were characterized by ^(1)H NMR and high-resolution mass spectrometry.The preliminary results of biological activity assessment indicated that some title compounds exhibited moderate to good insecticidal activities against oriental armyworm(Pseudaletia separata Walker).In particular,Va gave higher activity against oriental armyworm and diamondback moth.The present work reported that the new trifluoromethylated diamides incorporating N-trifluoroacetylsulfoximinyl moieties are potential lead compounds for further structure optimization,providing some insight into the relating structure-activity relationship.展开更多
In order to search for potent and environmental friendly insecticides with new modes of action, a series of pyranoside derivatives mimicking D-myo-inositol 1,4,5-trisphosphate (IP3) were designed and synthesized acc...In order to search for potent and environmental friendly insecticides with new modes of action, a series of pyranoside derivatives mimicking D-myo-inositol 1,4,5-trisphosphate (IP3) were designed and synthesized according to the bioisosterie approach. The biological assay indicated that most of the new compounds showed moderate to good insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (PluteIla xylostella). Especially, compound 5g displayed 80% larvicidal activity against oriental armyworm at 50 mg/L. Meanwhile, 5a showed 100% and 70% larvicidal activities against diamondback moth at 50 and 25 nag/L, respectively. To further explore the mode of action, calcium imaging technique was applied to study the effects of 5a, 5g, and 5i on the intracellular calcium ion concentration ([Ca^2+]i) in central neurons isolated from Spodoptera exigua. The results indicated that the tested compounds released stored calcium ions from endoplasmic reticulum.展开更多
The sulfoximine group has been evaluated as a pharmacophore. Introducing the sulfoximine structure into medicinal compounds as exciting motifs has brought opportunities in drug discovery. In order to develop new ryano...The sulfoximine group has been evaluated as a pharmacophore. Introducing the sulfoximine structure into medicinal compounds as exciting motifs has brought opportunities in drug discovery. In order to develop new ryanodine receptor (RyR) modulators, a series of phthalamides containing sulfoximine derivatives were designed, synthesized, and evaluated against oriental armyworm and diamondback moth for their insecticidal activities. These studies helped to elucidate the electronic and structural requirements around the sulfoximine motif for insecticidal activity. All new structures were synthesized and characterized by ^1H NMR, ^13C NMR, HRMS and bioassay and a preliminary structure-activity relationship (SAR) was discussed. The biological assessment indicated that most title compounds showed good to excellent larvicidal activities. Compounds la, le, and If gave excellent insecticidal activity against oriental armyworm, which showed 100% larvicidal activity at 0.5 mg/L. All compounds showed 100% larvicidal activity at 0.1 mg/L against diamondback moth. In particular, the larvicidal activities of le, If, and lh at 0.0001 mg/L were 50%, 20%, and 40%, respectively, reaching an activity as high as that of the commercial flubendiamide (40%, 0.0001mg/L). Therefore, Ia, Ie, If and Ih could be considered as new lead structures for the development of new ryanodine receptor (RyR) modulators.展开更多
A convenient and practicable method for the synthesis of the novel 2-(trifluoromethyl)-6-arylimidazo[2,1-b][1,3,4]-thiadiazole (bis-)Mannich base derivatives containing various substitutedpiperazine motif has been...A convenient and practicable method for the synthesis of the novel 2-(trifluoromethyl)-6-arylimidazo[2,1-b][1,3,4]-thiadiazole (bis-)Mannich base derivatives containing various substitutedpiperazine motif has been developed based on the fused-heterocycle intermediate. The new structures were identified through melting points, ^1H NMR, ^13C NMR, ^19F NMR, elemental analysis (or HRMS) and X-ray single-crystal diffraction. The pesticidal bioassays showed that some of compounds exhibited good fungicidal activities against Cercospora arachidicola, Physalospora piricola and Rhizoctonia cereali at 50 mg/L; some of them displayed favourable insecticidal activities against oriental armyworm (Mythimna separata Walker) at 200 rag/L, particularly, Vk and Vm with mortality rate of 75% and 80% respectively, could be considered as new insecticidal lead compounds for further structural optimization.展开更多
The issue of sensitivity attenuation in high-pressure region has been a persistent concern for pressure-sensitive electronic skins.In order to tackle such trade-off between sensitivity and linear range,herein,a hybrid...The issue of sensitivity attenuation in high-pressure region has been a persistent concern for pressure-sensitive electronic skins.In order to tackle such trade-off between sensitivity and linear range,herein,a hybrid piezoresistive-supercapacitive(HRSC)strategy is proposed via introducing a piezoresistive porous aerogel layer between the charge collecting electrodes and iontronic films of the pressure sensors.Surprisingly,the HRSC-induced impedance regulation and supercapacitive behavior contribute to significant mitigation in sensitivity attenuation,achieving high sensitivity across wide linear range(44.58 kPa^(−1)from 0 to 3 kPa and 23.6 kPa^(−1)from 3 to 12 kPa).The HRSC pressure sensor exhibits a low detection limit of 1 Pa,fast responsiveness(~130 ms),and excellent cycling stability,allowing to detect tiny pressure of air flow,finger bending,and human respiration.Meanwhile,the HRSC sensor exhibits exceptional perception capabilities for proximity and temperature,broadening its application scenarios in prosthetic perception and electronic skin.The proposed HRSC strategy may boost the ongoing research on structural design of high-performance and multimodal electronic sensors.展开更多
基金financially supported by the National Science and Technology Major Project(No.2017-VI-0008-0078)the Joint Fund of the National Natural Science Foundation of China and Baosteel Group Corporation(No.U1560106)+1 种基金the Aeronautical Science Foundation of China(No.2016ZF51050)the Scientific Research Foundation for the Returned Overseas Chinese Scholars(State Education Ministry)。
文摘At present,developing high-efficiency microwave absorption materials with properties including lightweight,thin thickness,strong absorbing intensity and broad bandwidth is an urgent demand to solve the electromagnetic pollution issues.An ideal microwave absorber should have excellent dielectric and magnetic loss capabilities,thereby inducing attenuation and absorption of incident electromagnetic radiation.Recently,various carbon/magnetic metal composites have been developed and expected to become promising candidates for high-performance microwave absorbers.In this review,we introduce the mechanisms of microwave absorption and summarize the recent advances in carbon/magnetic metal composites.Preparation methods and microwave absorption properties of carbon/magnetic metal composites with different components,morphologies and microstructures are discussed in detail.Finally,the challenges and future prospects of carbon/magnetic metal absorbing materials are also proposed,which will be useful to develop high-performance microwave absorption materials.
基金This work was financially supported by the National Natural Science Foundation of China (Nos. 21272129 and 21372133) and "111" Project of Ministry of Educa- tion of China (No. B06005). We also thank Prof. Er-Cai Shang and Dr. Yan-Jun Guo for their kind advices.
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 the National Natural Science Foundation of China(No.21772103)Tianjin Natural Science Foundation(No.17JCYBJC19900)the National Key Research and Development Program of China(No.2017YFD0200505)。
文摘A series of novel 1,2,4-oxadiazole-containing N-pyridylpyrazole derivatives 12 a-h were efficiently synthesized with pivaldehyde,pyridylpyrazole carboxylic acid and arylamine as raw materials via 1,3-dipolar cycloaddition.Their structures were identified by melting points,1 H NMR,13 C NMR and elemental analysis or HRMS.The exploration on the single-crystal structures of 12 c and 12 g revealed the stereochemical and substituent oriental characteristics,and the relevance of the structure and the reaction activity of this type of compounds.The preliminary bioassays indicated that several compounds had good insecticidal activities,among which 12 c showed a lethality rate of 80%towards Mythimna separata Walker at 200μg/mL;some of the compounds exhibited favorable fungicidal activities at 50μg/mL against Physalospora piricola,Rhizoctonia cereal,Sclerotinia sclerotiorum,etc.Among which,12 a,12 b,12 c and 12 h could be considered as new fungicidal leading compounds for further structural optimization.These discoveries along with the structure-activity relationship analysis in this paper will provide useful guidance for the innovative studies on new pyridylpyrazole derivatives and their applications in agrochemical area.
基金This work was financially supported by the National Natural Science Foundation of China (No. 21272129), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), and Syngenta Doctorate Scholarship.
文摘The study of soil degradation behaviors of sulfonylurea herbicides in relation to their different structural attributes is utmost important for us to comprehend the development of new eco-friendly herbicides. It is postulated that the structural modification of the chemical structures could influence their degradation rates in soil. Nine devised structures were synthesized to study their herbicidal activity as well as their soil degradation behaviors respectively. The novel compounds I-3-I-7 were characterized by UV, ^1H NMR and ^13C NMR, MS and EA. Bioassays indicated that most of target compounds displayed superior herbicidal activities in comparison with Chlorsulfuron. Soil degradation results further confirmed our previous assumption that the introduction of electron-donating substituents at 54 position of the benzene ring distinctly increased their degradation rates, among which dimethylamino and diethylamino groups can adjust the degradation rate to a more favorable status.
文摘A series of novel furan/thiophene and piperazine-containing 1,2,4-triazole Mannich bases and bis(1,2,4-triazole) Mannich bases have been conveniently synthesized via Mannich reaction with triazole Schiff bases, various pipera- zinc derivatives, and formaldehyde as intermediates in good yields. Their structures were characterized by melting points, ~H NMR, 13C NMR, IR and elemental analysis. The preliminary bioassay showed that most compounds ex- hibited significant in vitro and in vivo fungicidal activity against several test plant fungi. Among 32 new compounds, the trifluoromethyl-containing compounds showed superior activity than the methyl-containing ones. Several com- pounds, such as FS, F9, F10, G5, HT, 118, 13 and 14, were comparable with some commercial fungicides against different fungi during the present study and could be further structurally optimized. Meanwhile, several compounds showed good herbicidal activity against Brassica campestris at 100 ~tg/mL and KARl inhibitory activity at 200 μg/mL. However, compounds exhibited poor insecticidal activity against oriental armyworm at 200 μg/mL in the preliminary studies. The research results will provide useful information for the design and discovery of new agro- chemicals with novel heterocyclic structures.
文摘Two series of N-pyridylpyrazolecarboxamide derivatives were designed and synthesized by introducing D-alanine acid esters and D-serine acid esters into the skelecton of chlorantraniliprole. The obtained structures were characterized by 1H NMR, 13C NMR, elemental analysis and specific optical rotation analysis. Preliminary bioas-says indicated that some compounds displayed excellent insecticidal activities against Mythimna separate and Plutella xylostella in comparison with chlorantraniliprole. In particular, IIq showed excellent insecticidal activity against Plutella xylostella with a mortality rate of 90% at 0.01 mg·L^-1. A 3D-QSAR (CoMSIA) study was per- formed in order to disclose the insecticidal structure-activity relationship and indicate the future work. The CoMS1A study demonstrated that large substitutes and electron deficient groups at the 3-position of pyrazole ring are favora- ble, the same as a small group near the ester groups of amino acid.
基金financially supported by the National Key Research and Development Program of China(No.2017YFD0200505)the National Natural Science Foundation of China(No.21772103)Tianjin Natural Science Foundation(No.17JCYBJC19900)。
文摘A series of novel phenylpyrazole carboxylic acid derivatives containing fluorine moiety,i.e.,diamides 11,simple aryl-bearing amides 12 and acylthioureas 14 were successfully synthesized based on the key fluo ro-containing phe nylpyrazole acid intermediate.The new compounds were identified and confirmed by melting point,1H NMR,13C NMR and elemental analysis or HRMS.The bioassay results indicated that some of the compounds possessed excellent insecticidal activities towards oriental armyworm,diamondback moth and corn borer at low concentrations.For examples,compounds 11a,11e-g and 14b exhibited remarkable larvicidal activities with LC50 values of 0.13-0.39 mg/L and 0.0002-0.0014 mg/L against oriental armyworm and diamondback moth,respectively,were comparable with those of the control chlorantraniliprole.Particularly,lie were found superior to chlorantraniliprole in oriental armyworm tests(LC50:0.23 mg/L vs.0.26 mg/L);11a,lie,11f and 14c in diamondback moth tests with LC50 values of 0.0002 mg/L,0.0002 mg/L,0.0008 mg/L and 0.0005 mg/L,respectively,we re more effective than that of chlorantraniliprole.In addition,12 a also showed a promising insecticidal potential and development/optimization advantage.Compounds 11a,lle-g,12a,14b and 14c could be considered as possible new leading structures for further study.The SAR investigation indicated that the compounds with fluorine motif(e.g.,-F,-CF2H,-CF3)held apparently favorable insecticidal potentials,which provided useful guidance for further design/development of new phenylpyrazole-containing agrochemicals.
基金Project supported by the National Key Research and Development Program of China(No.2017YFD0200505)the National Natural Science Foundation of China(Nos.21772103 and 31972287)Tianjin Natural Science Foundation(No.17JCYBJC19900)。
文摘With the aim of discovering new bioactive pesticides for crop protection,a series of novel sulfidecontaining amide derivatives A were efficiently synthesized via a strategy of modifying the“amide”structure of anthranilic diamide insecticides.The single-crystal structures of A2-3 and A4-5 were firstly reported.The bioassay results showed that most of the synthesized compounds display moderate to high insecticidal activities.Particularly,some sulfone-containing compounds,e.g.,A2-3,A3-3 and A6-3,not only possessed favorable lethality rate(50%–100%)against P.xylostella at a concentration of 0.1 mg/L,but also held good activities towards a variety of agricultural pests such as M.separata,C.pipiens pallen,H.armigera and O.nubilalis;the larvicidal activities of A4-1 and A6-1 towards P.xylostella were close to that of chlorantraniliprole at 0.01 mg/L.The calcium imaging experiments revealed that the representative compounds A2-3 and A6-3 are potential ryanodine receptor(RyR)modulators.The structure–activity relationships were discussed in detail.These results provide useful information for further design and development of novel insecticides.
基金financially supported by the National Key Research and Development Program of China(No.2017YFD0200505)the National Natural Science Foundation of China(No.21772103)。
文摘Diamide compounds such as chlorantraniliprole,a famous anthranilic diamide insecticide targeting the insect ryanodine receptor(Ry R),have received continuous attention in pesticide research during the past 15 years owing to their excellent insecticidal potentials.With the aim of discovering new heterocyclic pesticides used for crop protection,based on the structural information of compound M from the reported pharmacophore-based virtual screening for Ry R insecticides and diamide compound,a series of new heterocyclic mono-,di-,and tri-amide derivatives containing piperazine moiety have been synthesized in this paper.The new compounds were identified and confirmed by melting point,^(1)H NMR,^(13)C NMR and HRMS.Compound M was firstly validated for insecticidal activities,and the new synthesized compounds were all made comprehensive insecticidal evaluations against diamondback moth and oriental armyworm.The bioassay results showed that some of the compounds exhibit favorable insecticidal potentials,particularly some novel piperazine-containing heterocyclic mono-/di-/tri-amide derivatives such as 8 g,14 a,15 a,15 g,15 i,15 j,15 k,15 l,and 15 m could be used as new insecticidal leading structures for further study(e.g.,towards diamondback moth,15i-15 m LC_(50):0.0022-0.0081 mg/L).The structure-activity relationships of the compounds discussed in detail provide useful guidance for further design and development of new insecticides.
基金This work was supported by Syngenta Postgraduate Fellowship,National Basic Research Program of China(No.2010CB126106)the National Key Technologies R&D Program(No.2011BAE06B05).
文摘Due to a novel mode action,low toxicity to mammals and low residue characteristics,phthalic acid diamides have aroused considerable interests in agricultural chemistry.With introduction of N-cyano,N-trifluoroacetyl,N-carbamoylsulfiliminyl and sulfoximinyl substituents into phthalamides,12 novel derivatives containing trifluoromethyl moiety were designed and synthesized.All title compounds were characterized by ^(1)H NMR and high-resolution mass spectrometry.The preliminary results of biological activity assessment indicated that some title compounds exhibited moderate to good insecticidal activities against oriental armyworm(Pseudaletia separata Walker).In particular,Va gave higher activity against oriental armyworm and diamondback moth.The present work reported that the new trifluoromethylated diamides incorporating N-trifluoroacetylsulfoximinyl moieties are potential lead compounds for further structure optimization,providing some insight into the relating structure-activity relationship.
基金This work was financially supported by the National Natural Science Foundation of China (No. 31370039), 973 Program (No. 2010CB 126106), the Tianjin Natural Science Foundation (No. 16JCYBJC29400) and the "111" Project of Ministry of Education of China (Project No. B06005).
文摘In order to search for potent and environmental friendly insecticides with new modes of action, a series of pyranoside derivatives mimicking D-myo-inositol 1,4,5-trisphosphate (IP3) were designed and synthesized according to the bioisosterie approach. The biological assay indicated that most of the new compounds showed moderate to good insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (PluteIla xylostella). Especially, compound 5g displayed 80% larvicidal activity against oriental armyworm at 50 mg/L. Meanwhile, 5a showed 100% and 70% larvicidal activities against diamondback moth at 50 and 25 nag/L, respectively. To further explore the mode of action, calcium imaging technique was applied to study the effects of 5a, 5g, and 5i on the intracellular calcium ion concentration ([Ca^2+]i) in central neurons isolated from Spodoptera exigua. The results indicated that the tested compounds released stored calcium ions from endoplasmic reticulum.
基金This work was supported by the National Natural Science Foundation of China (31370039, 21772103 and 21602118) and the Tianjin Natural Science Foundation (16JCYBJC29400 and 17JCYBJC19900).
文摘The sulfoximine group has been evaluated as a pharmacophore. Introducing the sulfoximine structure into medicinal compounds as exciting motifs has brought opportunities in drug discovery. In order to develop new ryanodine receptor (RyR) modulators, a series of phthalamides containing sulfoximine derivatives were designed, synthesized, and evaluated against oriental armyworm and diamondback moth for their insecticidal activities. These studies helped to elucidate the electronic and structural requirements around the sulfoximine motif for insecticidal activity. All new structures were synthesized and characterized by ^1H NMR, ^13C NMR, HRMS and bioassay and a preliminary structure-activity relationship (SAR) was discussed. The biological assessment indicated that most title compounds showed good to excellent larvicidal activities. Compounds la, le, and If gave excellent insecticidal activity against oriental armyworm, which showed 100% larvicidal activity at 0.5 mg/L. All compounds showed 100% larvicidal activity at 0.1 mg/L against diamondback moth. In particular, the larvicidal activities of le, If, and lh at 0.0001 mg/L were 50%, 20%, and 40%, respectively, reaching an activity as high as that of the commercial flubendiamide (40%, 0.0001mg/L). Therefore, Ia, Ie, If and Ih could be considered as new lead structures for the development of new ryanodine receptor (RyR) modulators.
基金This work was supported by the National Key Research and Development Program of China (No. 2017YFD0200505), the National Natural Science Foundation of China (Nos. 21372133 and 21772103), and Tianjin Natural Science Foundation (No. 17JCYBJC19900). We thank the teachers of the Biological Assay Center, Nankai University, for kind bioassay assistance of compounds.
文摘A convenient and practicable method for the synthesis of the novel 2-(trifluoromethyl)-6-arylimidazo[2,1-b][1,3,4]-thiadiazole (bis-)Mannich base derivatives containing various substitutedpiperazine motif has been developed based on the fused-heterocycle intermediate. The new structures were identified through melting points, ^1H NMR, ^13C NMR, ^19F NMR, elemental analysis (or HRMS) and X-ray single-crystal diffraction. The pesticidal bioassays showed that some of compounds exhibited good fungicidal activities against Cercospora arachidicola, Physalospora piricola and Rhizoctonia cereali at 50 mg/L; some of them displayed favourable insecticidal activities against oriental armyworm (Mythimna separata Walker) at 200 rag/L, particularly, Vk and Vm with mortality rate of 75% and 80% respectively, could be considered as new insecticidal lead compounds for further structural optimization.
基金the National Natural Science Foundation of China(Nos.22104021,52303075,and 22309105)Natural Science Foundation of Shandong Province(No.ZR2023QB227)+1 种基金Department of Science and Technology of Guangdong Province(No.2022A1515110014)Taishan Young Scholar Program(Nos.tsqn202306267 and tsqnz20231235).
文摘The issue of sensitivity attenuation in high-pressure region has been a persistent concern for pressure-sensitive electronic skins.In order to tackle such trade-off between sensitivity and linear range,herein,a hybrid piezoresistive-supercapacitive(HRSC)strategy is proposed via introducing a piezoresistive porous aerogel layer between the charge collecting electrodes and iontronic films of the pressure sensors.Surprisingly,the HRSC-induced impedance regulation and supercapacitive behavior contribute to significant mitigation in sensitivity attenuation,achieving high sensitivity across wide linear range(44.58 kPa^(−1)from 0 to 3 kPa and 23.6 kPa^(−1)from 3 to 12 kPa).The HRSC pressure sensor exhibits a low detection limit of 1 Pa,fast responsiveness(~130 ms),and excellent cycling stability,allowing to detect tiny pressure of air flow,finger bending,and human respiration.Meanwhile,the HRSC sensor exhibits exceptional perception capabilities for proximity and temperature,broadening its application scenarios in prosthetic perception and electronic skin.The proposed HRSC strategy may boost the ongoing research on structural design of high-performance and multimodal electronic sensors.