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1.
J Agric Food Chem ; 67(44): 12182-12190, 2019 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-31609606

RESUMO

In continuation of our program to develop natural-product-based pesticidal candidates, matrinic/oxymatrinic amides were obtained through structural optimization of matrine. N'-(4-Fluoro)phenyl-N-(4-bromo)phenylsulfonyloxymatrinic amide (IIm) showed potent insecticidal activity against Mythimna separata. N-(Un)substituted phenylsulfonylmatrinic acids (3a-c) exhibited promising acaricidal activity against Tetranychus cinnabarinus. By qRT-PCR analysis of nAChR subunits and AChE genes and determination of AChE activity of (un)treated T. cinnabarinus, it suggested that the open lactam ring of matrine and carboxyl group and (4-methyl)phenylsulfonyl of N-(4-methyl)phenylsulfonylmatrinic acid (3b) were necessary for action with α2, α4, α5, and ß3 nAChR subunits; compound 3b was an inhibitor of AChE in T. cinnabarinus, and AChE was one possible target of action in T. cinnabarinus against 3b; and compound 3b may be an antagonist of nAChR and AChE in T. cinnabarinus.


Assuntos
Acaricidas/química , Alcaloides/química , Amidas/química , Inseticidas/química , Quinolizinas/química , Acaricidas/síntese química , Acaricidas/farmacologia , Acetilcolinesterase/genética , Acetilcolinesterase/metabolismo , Alcaloides/farmacologia , Amidas/farmacologia , Animais , Inibidores da Colinesterase/síntese química , Inibidores da Colinesterase/química , Feminino , Proteínas de Insetos/genética , Proteínas de Insetos/metabolismo , Inseticidas/síntese química , Inseticidas/farmacologia , Estrutura Molecular , Mariposas/efeitos dos fármacos , Mariposas/genética , Mariposas/crescimento & desenvolvimento , Mariposas/metabolismo , Quinolizinas/farmacologia , Relação Estrutura-Atividade , Tetranychidae/efeitos dos fármacos , Tetranychidae/genética , Tetranychidae/crescimento & desenvolvimento , Tetranychidae/metabolismo
2.
J Agric Food Chem ; 67(40): 10997-11004, 2019 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-31487170

RESUMO

The enantioselective bioactivity, toxicity, and environmental behaviors of isocarbophos (ICP) were investigated. The order of the bioactivity and toxicity was S-(+) ≥ rac > R-(-), and the difference of R-(-) and S-(+) was up to 232 times. The usage of S-(+)-ICP may efficiently reduce the usage amount of rac-ICP by 35% under the same effect, and the toxicity was not increased. Based on the toxic unit analysis, the additive effect and synergistic effect of ICP enantiomers were found in the four nontarget organisms, and R-(-)-ICP might cooperate the side-effects of S-(+)-ICP. The accumulation of rac-ICP in earthworms was enantioselective with an enantioenrichment of R-(-)-ICP, so the usage of racemic ICP might increase the exposure risk of R-(-)-ICP to earthworms. From the comprehensive results, the production of enantiomer enriched S-(+)-ICP might increase bioactivity and reduce environmental pollution, while the toxicity of S-(+)-ICP to other nontarget organisms needs to be further assessed.


Assuntos
Inseticidas/química , Inseticidas/toxicidade , Malation/análogos & derivados , Animais , Malation/química , Malation/toxicidade , Oligoquetos/efeitos dos fármacos , Oligoquetos/crescimento & desenvolvimento , Estereoisomerismo , Relação Estrutura-Atividade
3.
J Agric Food Chem ; 67(39): 10977-10983, 2019 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-31490679

RESUMO

In this study, an analytical method was developed and validated for simultaneous determination of five diamide insecticides (chlorantraniliprole, cyantraniliprole, flubendiamide, cyclaniliprole, and tetrachlorantraniliprole) in food matrices. Determination of the latter two diamide compounds is first reported. Samples were cleaned up by multiplug filters containing carbon nanotubes (CNT) or hydrophilic-lipophilic balanced copolymers (HLB) and classic dispersive solid phase extraction (d-SPE) procedures, respectively. The CNT multiplug filter performed the best in terms of process rapidity and cleanup efficiency; thus, it was finally chosen for sample cleanup. Instrumental analysis was completed in 5 min using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Mean recoveries of the five diamides ranged from 84.3 to 110.0%, with intraday and interday relative standard deviations (RSD) of less than 13.5%. Limits of quantitation (LOQ) of all analytes ranged from 0.005 to 0.01 mg kg-1 in different matrices. The results indicate this method is reliable for monitoring the five diamide insecticides in various foods.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Diamida/química , Filtração/métodos , Contaminação de Alimentos/análise , Inseticidas/química , Resíduos de Praguicidas/química , Espectrometria de Massas em Tandem/métodos , Diamida/isolamento & purificação , Filtração/instrumentação , Inseticidas/isolamento & purificação , Nanotubos de Carbono/química , Resíduos de Praguicidas/isolamento & purificação
4.
J Agric Food Chem ; 67(37): 10498-10504, 2019 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-31452369

RESUMO

Owing to the changing needs of agriculture, the exploration of new pest control agents remains as critical as ever. The analogues 3a-3v of the natural product cerbinal were synthesized from genipin by an efficient and practical method under additive-free conditions. The antiviral and insecticidal effects of cerbinal and these cyclopenta[c]pyridines (3a-3v) were evaluated systematically. Most of the synthesized compounds exhibited higher anti-TMV activities than the lead compound cerbinal. Compound 3s (2-(4-methoxyphenyl)) had the most promising inhibitory activities against TMV (inactivation effect 49.0 ± 0.8%, curative effect 41.2 ± 4.3%, and protection effect 51.5 ± 2.7% at 500 µg/mL). Among the synthesized compounds, only 3v (2-(2-chloro-4-(trifluoromethoxy)phenyl)) reached the activity level of cerbinal against Plutella xylostella. This suggested that the cyclopenta[c]pyridines obtained by modifications of cerbinal at position 2 are very significant for the anti-TMV activity, and yet were exceptionally less active for the insecticidal activities.


Assuntos
Antivirais/síntese química , Antivirais/farmacologia , Produtos Biológicos/síntese química , Produtos Biológicos/farmacologia , Indenos/química , Indenos/farmacologia , Inseticidas/química , Inseticidas/farmacologia , Animais , Antivirais/química , Produtos Biológicos/química , Descoberta de Drogas , Indenos/síntese química , Inseticidas/síntese química , Iridoides/química , Estrutura Molecular , Mariposas/efeitos dos fármacos , Mariposas/crescimento & desenvolvimento , Piridinas/síntese química , Piridinas/química , Piridinas/farmacologia , Relação Estrutura-Atividade , Vírus do Mosaico do Tabaco/efeitos dos fármacos , Vírus do Mosaico do Tabaco/crescimento & desenvolvimento
5.
J Agric Food Chem ; 67(36): 10032-10041, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31419121

RESUMO

Flonicamid (N-cyanomethyl-4-trifluoromethylnicotinamide, FLO), a novel selective systemic pyridinecarboxamide insecticide, effectively controls hemipterous pests. However, microbial degradation of flonicamid, along with the enzymatic mechanism, has not been studied. Here, bacterial isolate PG13, which converts flonicamid into 4-(trifluoromethyl)nicotinol glycine (TFNG) and N-(4-trifluoromethylnicotinoyl)glycinamide (TFNG-AM), was isolated and identified as Alcaligenes faecalis CGMCC 17553. The genome of CGMCC 17553 contained five nitrilases but no nitrile hydratase, and recombinant Escherichia coli strains harboring CGMCC 17553 nitrilase gene nitA or nitD acquired the ability to degrade flonicamid. Purified NitA catalyzed flonicamid into both TFNG and TFNG-AM, indicating dual functionality, while NitD could only produce TFNG-AM. Three-dimensional homology modeling revealed that aromatic amino acid residues in the catalytic pocket affected nitrilase activity. These findings further our understanding of the enzymatic mechanism of flonicamid metabolism in the environment and may help develop a potential bioremediation agent for the elimination of flonicamid contamination.


Assuntos
Alcaligenes faecalis/metabolismo , Aminoidrolases/metabolismo , Proteínas de Bactérias/metabolismo , Inseticidas/metabolismo , Niacinamida/análogos & derivados , Alcaligenes faecalis/enzimologia , Alcaligenes faecalis/genética , Aminoidrolases/genética , Proteínas de Bactérias/genética , Biocatálise , Biodegradação Ambiental , Hidrólise , Inseticidas/química , Niacinamida/química , Niacinamida/metabolismo
6.
J Agric Food Chem ; 67(33): 9362-9370, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31368700

RESUMO

This manuscript presents an effective and robust method for simultaneous stereoselective determination of two pyrethroid insecticides, tetramethrin and α-cypermethrin in different food products by high-performance liquid chromatography. Enantioseparation was carried out using reversed-phase chromatography, and the influences of four polysaccharide-based chiral columns, mobile phase composition, and column temperature on retention were fully investigated. Satisfactory separation was obtained on Chiralpak IG column using acetonitrile-water (75:25, v/v) under isocratic conditions. To extract and purify the target analytes from food matrices, matrix solid-phase dispersion was employed with C18 as dispersant and primary secondary amine as well as graphitized carbon black as cleanup sorbents. Response surface method based on Box-Behnken design was implemented to assist optimization of the extraction variables. Then, method validation was done in real samples including specificity, linearity, sensitivity, trueness, precision, as well as stability, and its analytical performance fulfills the criteria recommended by the European Union SANTE/11945/2015, demonstrating its applicability in studying the stereochemistry of chiral tetramethrin and α-cypermethrin in food products.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Grão Comestível/química , Frutas/química , Inseticidas/química , Piretrinas/química , Verduras/química , Cromatografia de Fase Reversa/métodos , Contaminação de Alimentos/análise , Inseticidas/isolamento & purificação , Piretrinas/isolamento & purificação , Extração em Fase Sólida , Estereoisomerismo
7.
J Agric Food Chem ; 67(33): 9210-9219, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31390203

RESUMO

The insecticidal and antifeedant activities of five 7-chloro-4-(1H-1,2,3-triazol-1-yl)quinoline derivatives were evaluated against the maize armyworm, Spodoptera frugiperda (J.E. Smith). These hybrids were prepared through a copper-catalyzed azide alkyne cycloaddition (CuAAC, known as a click reaction) and displayed larvicidal properties with LD50 values below 3 mg/g insect, and triazolyl-quinoline hybrid 6 showed an LD50 of 0.65 mg/g insect, making it 2-fold less potent than methomyl, which was used as a reference insecticide (LD50 = 0.34 mg/g insect). Compound 4 was the most active antifeedant derivative (CE50 = 162.1 µg/mL) with a good antifeedant index (56-79%) at concentrations of 250-1000 µg/mL. Additionally, triazolyl-quinoline hybrids 4-8 exhibited weak inhibitory activity against commercial acetylcholinesterase from Electrophorus electricus (electric-eel AChE) (IC50 = 27.7 µg/mL) as well as low anti-ChE activity on S. frugiperda larvae homogenate (IC50 = 68.4 µg/mL). Finally, molecular docking simulations suggested that hybrid 7 binds to the catalytic active site (CAS) of this enzyme and around the rim of the enzyme cavity, acting as a mixed (competitive and noncompetitive) inhibitor like methomyl. Triazolyl-quinolines 4-6 and 8 inhibit AChE by binding over the perimeter of the enzyme cavity, functioning as noncompetitive inhibitors. The results described in this work can help to identify lead triazole structures from click chemistry for the development of insecticide and deterrent products against S. frugiperda and related insect pests.


Assuntos
Inseticidas/síntese química , Inseticidas/farmacologia , Larva/efeitos dos fármacos , Quinolinas/química , Quinolinas/farmacologia , Spodoptera/efeitos dos fármacos , Acetilcolinesterase/química , Acetilcolinesterase/metabolismo , Animais , Inibidores da Colinesterase/síntese química , Inibidores da Colinesterase/química , Inibidores da Colinesterase/farmacologia , Química Click , Simulação por Computador , Proteínas de Insetos/antagonistas & inibidores , Proteínas de Insetos/química , Proteínas de Insetos/metabolismo , Inseticidas/química , Larva/enzimologia , Larva/crescimento & desenvolvimento , Simulação de Acoplamento Molecular , Doenças das Plantas/parasitologia , Spodoptera/enzimologia , Spodoptera/crescimento & desenvolvimento , Zea mays/parasitologia
8.
J Agric Food Chem ; 67(36): 9989-9999, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31430135

RESUMO

Zein's prevalent hydrophobic character is one of the major challenges associated with ineffective utilization as an aqueous nanocarrier for pesticides. Herein, we report an effective approach to hydrophilic modification of zein by phosphorylation using nontoxic sodium tripolyphosphate (STP), thereby improving the water-solubility, foliage wettability, and adhesion ability of zein as a nanocarrier for sustained release of pesticides. The procedure relied on zein grafted with STP via N- and O- phosphate bonds and encapsulation of avermectin (AVM) as a hydrophobic model drug using phosphorylated zein (P-Zein), which achieved pH sensitivity to controlled release of AVM in various applicable environments. The chemical interaction between zein and STP was confirmed by Fourier transform infrared, thermogravimetric analysis, and differential scanning calorimetric. Scanning electron microscopy, dynamic light scattering, and zeta potential technique were applied to investigate their structural characteristics and stability, from which it was found that AVM encapsulated in P-Zein (AVM@P-Zein) formed uniform nanoparticles with average sizes in the range of 174-278 nm under different conditions, and had an excellent stability in aqueous solution. Besides, AVM@P-Zein facilitated the wettability on the foliage surface evidenced from contact angle values owing to the amphiphilic character after phosphorylation as well as enhanced the adhesion ability between liquid and leaf, restricting the pesticide runoff. Ultraviolet-visible spectroscopy was employed to explore the anti-UV property and encapsulation as well as release behavior, which revealed that the presence of P-Zein like a shell protects AVM from UV photolysis with encapsulation efficiency of approximately 81.52%, and the release of AVM from P-Zein showed pH-responsive behavior ascribed to protonation and deprotonation of phosphate under various pH conditions fitting to Elovich kinetic model, achieving the relatively more rapid release under acidic conditions. More importantly, AVM@P-Zein retained the toxicity for insecticidal effect.


Assuntos
Preparações de Ação Retardada/química , Portadores de Fármacos/química , Composição de Medicamentos/métodos , Inseticidas/química , Ivermectina/análogos & derivados , Nanopartículas/química , Zeína/química , Animais , Preparações de Ação Retardada/farmacologia , Portadores de Fármacos/efeitos da radiação , Composição de Medicamentos/instrumentação , Concentração de Íons de Hidrogênio , Interações Hidrofóbicas e Hidrofílicas , Inseticidas/farmacologia , Ivermectina/química , Ivermectina/farmacologia , Cinética , Mariposas/efeitos dos fármacos , Mariposas/crescimento & desenvolvimento , Nanopartículas/efeitos da radiação , Fosforilação , Polifosfatos/química , Raios Ultravioleta , Zeína/efeitos da radiação
9.
Toxicol Lett ; 314: 124-132, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31362050

RESUMO

Organophosphates are chemical pollutants that are existed widely in the environment, but the reactions of these agents with blood proteins are still not fully clarified. The current story was to analyze the static and dynamic interactions between human serum albumin (HSA) and phenthoate and then uncover the impact of the conjugations on the acetylcholinesterase (AChE) activity at the microscopic scale. Experimental results revealed clearly that the bioconjugate of the HSA-phenthoate was yielded and the conformation of HSA can produce autoregulation during the reaction. Dynamic reaction processes suggested that the conformational flexibility of the specific protein domain was changed significantly in equilibrium, and the electrostatic interaction energy played a major role in total energy of the biosystems, which matches the results of wet experiment and molecular docking. We also found that the modes of homologous proteins-phenthoate have obvious distinctions, and this point is related closely to the local dynamic flexibility of biomolecular structures. Additionally, the degree of bioconjugation of the HSA-phenthoate is positively associated with the enzymatic activity of target AChE, which may be attributed to the competitive reactions between HSA and AChE. Evidently, this scenario could provide useful molecular information for the systematic exploration of the toxicokinetics of organophosphorus compounds.


Assuntos
Inibidores da Colinesterase/sangue , Inseticidas/sangue , Modelos Biológicos , Simulação de Acoplamento Molecular , Compostos Organotiofosforados/sangue , Albumina Sérica Humana/metabolismo , Acetilcolinesterase/química , Acetilcolinesterase/metabolismo , Sítios de Ligação , Ligação Competitiva , Inibidores da Colinesterase/química , Inibidores da Colinesterase/toxicidade , Humanos , Inseticidas/química , Inseticidas/toxicidade , Compostos Organotiofosforados/química , Compostos Organotiofosforados/toxicidade , Ligação Proteica , Conformação Proteica , Domínios Proteicos , Albumina Sérica Humana/química
10.
J Agric Food Chem ; 67(29): 8130-8137, 2019 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-31287295

RESUMO

Chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was granted supplemental registration for use in rice cultivation in California through December, 2018. Previous work investigated the partitioning of CAP in California rice field soils; however, its degradation in soils under conditions relevant to California rice culture has not been investigated. The degradation of CAP in soils from two California rice fields was examined under aerobic and anaerobic conditions with varying salinity via microcosm experiments. Results indicate that soil properties governing bioavailability may have a greater influence on degradation than flooding practices or field salinization over a typical growing season. Differences between native and autoclaved soils (t1/2 = 59.0-100.2 and 78.5-171.7 days) suggest that biological processes were primarily responsible for CAP degradation; however, future work should be done to confirm specific biotic processes as well as to elucidate abiotic processes, such as degradation via manganese oxides and formation of nonextractable residues, which may contribute to its dissipation.


Assuntos
Inseticidas/química , Oryza/crescimento & desenvolvimento , Poluentes do Solo/química , Solo/química , ortoaminobenzoatos/química , Agricultura , California , Inundações , Cinética
11.
J Agric Food Chem ; 67(31): 8573-8580, 2019 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-31293156

RESUMO

Glycosylation endows both natural and synthetic small molecules with modulated physicochemical and biological properties. Plant and bacterial glycosyltransferases capable of decorating various privileged scaffolds have been extensively studied, but those from kingdom Fungi still remain underexploited. Here, we use a combination of genome mining and heterologous expression techniques to identify four novel glycosyltransferase-methyltransferase (GT-MT) functional modules from Hypocreales fungi. These GT-MT modules display decent substrate promiscuity and regiospecificity, methylglucosylating a panel of natural products such as flavonoids, stilbenoids, anthraquinones, and benzenediol lactones. Native GT-MT modules can be split up and regrouped into hybrid modules with similar or even improved efficacy as compared with native pairs. Methylglucosylation of kaempferol considerably improves its insecticidal activity against the larvae of oriental armyworm Mythimna separata (Walker). Our work provides a set of efficient biocatalysts for the combinatorial biosynthesis of small molecule glycosides that may have significant importance to the pharmaceutical, agricultural, and food industries.


Assuntos
Proteínas Fúngicas/química , Glicosiltransferases/química , Hypocreales/enzimologia , Metiltransferases/química , Fenóis/química , Animais , Biocatálise , Cristalografia por Raios X , Proteínas Fúngicas/genética , Proteínas Fúngicas/metabolismo , Glicosilação , Glicosiltransferases/genética , Glicosiltransferases/metabolismo , Hypocreales/genética , Inseticidas/química , Inseticidas/farmacologia , Metilação , Metiltransferases/genética , Metiltransferases/metabolismo , Mariposas/efeitos dos fármacos , Fenóis/farmacologia , Especificidade por Substrato
12.
Environ Pollut ; 252(Pt B): 1593-1598, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31279977

RESUMO

Exploring traditional neonicotinoid pesticides substitutes has become one of the global scientific attentions because of their hazardous environmental impacts. Cycloxaprid (CYC) is considered to be a promising candidate alternative. But the environmental behaviors and fate of CYC in different planting system remain poorly understood. The accumulation of 14C-labeled CYC stereoisomers within different parts of Chinese cabbage (Brassica chinensis L.) was investigated, with a particular focus on the foliar absorption, translocation and stereoselectivity of CYC, during a laboratory trial. In general, the stereoisomers 14C-5R,8S-CYC and 14C-5S,8R-CYC, their metabolites, as well as the breakdown and reaction products can be transferred in both acropetal and basipetal directions. Most of the two stereoisomers absorbed by plants remained in the treated leaves, whereas a small amount was distributed to the roots. The amount of 14C in the stalks varied among the experimental time points. At 192 h after treatment (HAT), the detected radioactivity of both 14C-5R,8S-CYC and 14C-5S,8R-CYC in the leaves above the treated leaf (LATL) was higher than that in the leaves below the treated leaf (LBTL). However, the stereoisomers of CYC underwent nonstereoselective absorption and translocation in this trial. This information implies that racemic CYC and its metabolites should be a main research focus. Thus, the obtained results provide implications for a more accurate prediction about the risk assessment of CYC, which will be helpful for guiding its rational use as well as securing the ecological environment safety and human health.


Assuntos
Brassica/metabolismo , Compostos Heterocíclicos com 3 Anéis/metabolismo , Inseticidas/metabolismo , Neonicotinoides/metabolismo , Folhas de Planta/metabolismo , Piridinas/metabolismo , Transporte Biológico , Compostos Heterocíclicos com 3 Anéis/química , Inseticidas/química , Modelos Teóricos , Neonicotinoides/química , Raízes de Plantas/metabolismo , Piridinas/química , Estereoisomerismo
13.
J Enzyme Inhib Med Chem ; 34(1): 1226-1232, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31307248

RESUMO

Allosamidins come from the secondary metabolites of Streptomyces species, and they have the pseudotrisaccharide structures. Allosamidins are chitinase inhibitors that can be used to study the physiological effects of chitinases in a variety of organisms. They have the novel antiasthmatic activity and insecticidal/antifungal activities. Herein, the synthesis and activities of allosamidins were summarized and analyzed.


Assuntos
Acetilglucosamina/análogos & derivados , Antiasmáticos/farmacologia , Antifúngicos/farmacologia , Inseticidas/farmacologia , Trissacarídeos/farmacologia , Acetilglucosamina/química , Acetilglucosamina/isolamento & purificação , Acetilglucosamina/farmacologia , Animais , Antiasmáticos/química , Antiasmáticos/isolamento & purificação , Antifúngicos/química , Antifúngicos/isolamento & purificação , Asma/tratamento farmacológico , Fungos/efeitos dos fármacos , Humanos , Inseticidas/química , Inseticidas/isolamento & purificação , Conformação Molecular , Mariposas/efeitos dos fármacos , Streptomyces/química , Trissacarídeos/química , Trissacarídeos/isolamento & purificação
14.
J Agric Food Chem ; 67(28): 7793-7809, 2019 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-31274315

RESUMO

Indoxacarb, a commercialized oxadiazine insecticide, nearly irreversibly blocks open/inactivated, but not resting sodium channels. The structure-activity relationships showed that the substituents at the position of the chiral atom in the oxadiazine ring are very important to the biological activity of oxadiazine insecticide. Here we synthesized a series of tricyclic oxadiazine 4a-methyl ester derivatives. The chiral atom in the oxadiazine ring has been epimerized and substituted with either pyrethric acid or cinnamic acid derivatives. Benzene ring in the tricyclic moiety was substituted with a chlorine, fluorine, or bromine atom, and nitrogen-linked benzene ring was substituted with a trifluoromethyl or trifluoromethoxy group. Toxicity of these compounds against Spodoptera litura F. was evaluated. Diastereoisomers of most toxic compounds J7 and J9 with pyrethric acid moiety were separated by flash column chromatography. The more polar diastereoisomers, J7-L-Rf and J9-L-Rf, and compounds J24 and J26 with cinnamic acid moiety exhibited highest insecticidal activities. We further used Monte Carlo energy minimizations to dock compound J7 and J24 in the NavMs-based homology model of the open cockroach sodium channel. In the low-energy binding modes, the compound interacted with residues in the inner pore and domain interfaces, which previously were proposed to contribute to receptors of pyrethroids and sodium channel blocker insecticides. Our results define compound J7 and J24 as a potentially useful optimized hit for the development of multiple sites sodium channel blocker or modulator.


Assuntos
Inseticidas/química , Inseticidas/toxicidade , Oxazinas/química , Oxazinas/toxicidade , Bloqueadores dos Canais de Sódio/química , Bloqueadores dos Canais de Sódio/toxicidade , Animais , Baratas/efeitos dos fármacos , Baratas/metabolismo , Descoberta de Drogas , Ésteres/química , Ésteres/farmacologia , Proteínas de Insetos/química , Proteínas de Insetos/metabolismo , Modelos Moleculares , Canais de Sódio/química , Canais de Sódio/metabolismo , Spodoptera/efeitos dos fármacos , Spodoptera/metabolismo , Relação Estrutura-Atividade
15.
Anal Chim Acta ; 1074: 131-141, 2019 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-31159933

RESUMO

Semiconducting single-walled carbon nanotubes (s-SWCNTs) have been demonstrated as an excellent material for transistors, miniaturized devices and sensors due to their high carrier mobility, stability, scattering-free ballistic transport of carriers etc. Herein, we have designed a biosensor to selectively detect methyl parathion (MP, organophosphorus pesticide) using glutaraldehyde (Glu) cross-linked with acetylcholinesterase (AChE) immobilized on s-SWCNTs wrapped with bovine serum albumin (BSA). The fabricated biosensor was characterized and confirmed by Fourier-transform infrared spectroscopy (FT-IR), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and square wave voltammetry (SWV). In the presence of MP, the effective interaction between AChE and MP favours the accumulation of MP-AChE complex on the glassy carbon electrode (GCE) surface which reduces the electron transfer property. Based on this interaction, detection of various concentration of MP was demonstrated by SWV using BSA/AChE-Glu-s-SWCNTs composite modified electrode. The proposed biosensor exhibited a wide linear range (WLR) for MP target in 100 mM phosphate buffered saline solution (PBS) (pH 7.4) from 1 × 10-10 M to 5 × 10-6 M with a limit of detection (LOD) of 3.75 × 10-11 M. In addition, the BSA/AChE-Glu-s-SWCNTs/GCE biosensor showed good repeatability and reproducibility for MP detection. Moreover, the proposed biosensor showed better electrode stability when stored at 4 °C. This new electrochemical biosensor is also exhibited high selectivity and sensitivity for MP, which made it possible to test MP in real strawberry and apple juices. Furthermore, the BSA/AChE-Glu-s-SWCNTs/GCE offered a favourable electron transfer between the acetylthiocholine chloride (ATCl) and electrode interface than BSA/AChE-s-SWCNTs/GCE, s-SWCNTs/GCE and bare GCE.


Assuntos
Acetilcolinesterase/química , Inseticidas/análise , Metil Paration/análise , Nanocompostos/química , Nanotubos de Carbono/química , Soroalbumina Bovina/química , Animais , Técnicas Biossensoriais/métodos , Carbono , Bovinos , Reagentes para Ligações Cruzadas/química , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Eletrodos , Electrophorus , Enzimas Imobilizadas/química , Contaminação de Alimentos/análise , Fragaria/química , Glutaral/química , Inseticidas/química , Limite de Detecção , Malus/química , Metil Paration/química , Reprodutibilidade dos Testes
16.
Environ Sci Pollut Res Int ; 26(24): 24988-24997, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31240663

RESUMO

Essential oils (EOs) extracted from leaves (EL) and fruit pericarp (EFP) of Zanthoxylum planispinum var. dintanensis were analyzed for their chemical composition by GC-MS technique and evaluated for their fumigant, contact toxicity and repellency against three stored-product insects, namely Tribolium castaneum, Lasioderma serricorne, and Liposcelis bostrychophila adults. Results of GC-MS analysis manifested that EL and EFP of Z. planispinum var. dintanensis were mainly composed of oxygenated monoterpenes. Major components included linalool, sylvestrene and terpinen-4-ol. The obvious variation observed between two oil samples was that EL contained 2-dodecanone (11.52%) in addition to the above mentioned components, while this constituent was not detected in EFP. Bioassays of insecticidal and repellent activities were performed for EL, EFP as well as some of their individual compounds (linalool, terpinen-4-ol and 2-dodecanone). Testing results indicated that EL, EFP, linalool, terpinen-4-ol and 2-dodecanone exhibited potent insecticidal and repellent activities against the three target insects selected. Among the three individual compounds, 2-dodecanone was significantly toxic to T. castaneum (LD50 = 5.21 µg/adult), L. serricorne (LD50 = 2.54 µg/adult) and L. bostrychophila (LD50 = 23.41 µg/cm2) in contact assays and had beneficial repellent effects on L. serricorne at 2 and 4 h post-exposure. The anti-insect efficacy of Z. planispinum var. dintanensis EO suggests it has potential to be used as botanical insecticide or repellent to control pest damage in warehouses and grain stores.


Assuntos
Repelentes de Insetos/farmacologia , Inseticidas/análise , Monoterpenos/química , Óleos Voláteis/química , Terpenos/química , Zanthoxylum/química , Animais , Besouros/efeitos dos fármacos , Cromatografia Gasosa-Espectrometria de Massas , Repelentes de Insetos/química , Inseticidas/química , Dose Letal Mediana , Monoterpenos/análise , Oxirredução , Tribolium/química
17.
J Agric Food Chem ; 67(26): 7538-7546, 2019 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-31180663

RESUMO

Thiamethoxam (TMX) has already been proven to have a physiological effect in plant tissue or cell expect for the insecticidal activity. In our previous study, TMX was verified to be metabolized by tea cells in either a suspension culture or tea plant into several metabolites. Here, tea cell suspension cultures were treated for 45 days to investigate the metabolite effects in both the tea cells and the culture supernatants by nontargeted metabolomics. Using multivariate analysis (PCA and OPLS-DA), all treatment and control groups could be clearly separated. Inside the cells, 113 metabolites were found to be up-regulated while 122 were down-regulated, when compared with untreated cells. In the culture supernatant, there were 128 up-regulated and 35 down-regulated metabolites, compared to untreated cultures. KEGG searches revealed that the alanine, aspartate, and glutamate metabolic pathways were strongly affected by TMX metabolism within the tea cell. Molecular docking models showed that (i) 4-aminobutyrate aminotransferase may be related to the formation of 2-chloro-thiazole-5-carboxylic acid and (ii) 3'(2'),5'-bisphosphate nucleotidase may be able to interact with TMX. This study can help us to understand the interaction mechanism of pesticides with plant cells.


Assuntos
Camellia sinensis/química , Camellia sinensis/metabolismo , Inseticidas/metabolismo , Tiametoxam/metabolismo , Células Cultivadas , Inseticidas/química , Redes e Vias Metabólicas , Metabolômica , Simulação de Acoplamento Molecular , Tiametoxam/química
18.
Pestic Biochem Physiol ; 157: 1-12, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-31153457

RESUMO

The use of neurotoxic chemical insecticides has led to consequences against the environment, insect resistances and side-effects on non-target organisms. In this context, we developed a novel strategy to optimize insecticide efficacy while reducing doses. It is based on nanoencapsulation of a pyrethroid insecticide, deltamethrin, used as synergistic agent, combined with a non-encapsulated oxadiazine (indoxacarb). In this case, the synergistic agent is used to increase insecticide efficacy by activation of calcium-dependant intracellular signaling pathways involved in the regulation of the membrane target of insecticides. In contrast to permethrin (pyrethroid type I), we report that deltamethrin (pyrethroid type II) produces an increase in intracellular calcium concentration in insect neurons through the reverse Na/Ca exchanger. The resulting intracellular calcium rise rendered voltage-gated sodium channels more sensitive to lower concentration of the indoxacarb metabolite DCJW. Based on these findings, in vivo studies were performed on the cockroach Periplaneta americana and mortality rates were measured at 24 h, 48 h and 72 h after treatments. Comparative studies of the toxicity between indoxacarb alone and indoxacarb combined with deltamethrin or nanoencapsulated deltamethrin (LNC-deltamethrin), indicated that LNC-deltamethrin potentiated the effect of indoxacarb. We also demonstrated that nanoencapsulation protected deltamethrin from esterase-induced enzymatic degradation and led to optimize indoxacarb efficacy while reducing doses. Moreover, our results clearly showed the benefit of using LNC-deltamethrin rather than piperonyl butoxide and deltamethrin in combination commonly used in formulation. This innovative strategy offers promise for increasing insecticide efficacy while reducing both doses and side effects on non-target organisms.


Assuntos
Cálcio/metabolismo , Inseticidas/química , Inseticidas/farmacologia , Nanocápsulas/química , Nitrilos/química , Nitrilos/farmacologia , Oxazinas/química , Oxazinas/farmacologia , Piretrinas/química , Piretrinas/farmacologia , Animais , Células Cultivadas , Baratas , Masculino , Estrutura Molecular , Periplaneta/efeitos dos fármacos , Trocador de Sódio e Cálcio/metabolismo
19.
Pestic Biochem Physiol ; 157: 122-137, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-31153459

RESUMO

Novel phospho guanidine and phospho pyrazine derivatives were synthesized and characterized by 31P, 13C, 1HNMR and IR spectroscopy to obtain novel and human-safe insecticides. Compound 35 [(C4H4N2NH)2P(O)(C6H6)] was investigated by X-ray crystallography. The inhibitory effects of synthesized compounds were evaluated on human and insect acetylcholinesterase (AChE) using in vitro Ellman method. A few of these compounds, which had low human toxicity, were selected for assessing the killing effects (in vivo) on the elm leaf beetle (X.luteola). The in vitro and in vivo results indicated that compounds bearing both phosphoryl groups and aromatic systems were found to possess a good selectivity for the inhibition of insect AChE over human AChE; up to 550-fold selectivity was achieved for compound 19. Docking studies were performed to explain reasons for the selective behavior of AChE inhibitors. Additionally, the quantitative structure-activity relationship (QSAR) and density functional theory (DFT) results of AChEs demonstrated that the size, shape, dipole moment, and ability to form hydrogen bond played the main role in both models. In addition, the aromatic π - π interactions and charge of the amide nitrogen had a major effect on insecticidal activity of the compounds. The present research can be helpful to gain a better understanding of the interactions between the insect AChE and its inhibitors and introduces compounds which are capable of becoming human-safe insecticides.


Assuntos
Inibidores da Colinesterase/química , Inibidores da Colinesterase/síntese química , Guanidinas/química , Pirazinas/química , Acetilcolinesterase/metabolismo , Animais , Inibidores da Colinesterase/farmacologia , Besouros/efeitos dos fármacos , Humanos , Inseticidas/síntese química , Inseticidas/química , Inseticidas/farmacologia , Simulação de Acoplamento Molecular , Estrutura Molecular , Relação Quantitativa Estrutura-Atividade , Relação Estrutura-Atividade
20.
J Agric Food Chem ; 67(20): 5891-5898, 2019 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-31059246

RESUMO

A study was carried out to evaluate the dissipation kinetics of field-applied omethoate during wheat storage. Both the identification and metabolic dynamics of omethoate metabolites were analyzed using UPLC-QTOF/MS. The presence of the metabolite dimethyl phosphate (DMP) was confirmed in wheat samples with applied omethoate. This might be because the group attached to the P atom of omethoate is replaced by a hydroxyl group through hydrolysis, thus leading to the formation of the specific metabolite DMP during wheat storage. Although the initial concentrations of DMP in different doses were considerably lower than those of omethoate, the half-life values of DMP were 11.87-31.50 days, which were close to the half-life of the parent omethoate (11.85-30.94 days). This indicates that potential health risks might be caused by dietary exposure to DMP and omethoate. Therefore, more importance should be given to the risk assessment for omethoate and its metabolite DMP in wheat.


Assuntos
Dimetoato/análogos & derivados , Inseticidas/química , Compostos Organofosforados/química , Triticum/química , Cromatografia Líquida de Alta Pressão , Dimetoato/química , Dimetoato/metabolismo , Contaminação de Alimentos/análise , Armazenamento de Alimentos , Inseticidas/metabolismo , Cinética , Compostos Organofosforados/metabolismo , Espectrometria de Massas em Tandem , Triticum/metabolismo
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