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1.
Cell ; 156(5): 950-62, 2014 Feb 27.
Artículo en Inglés | MEDLINE | ID: mdl-24581494

RESUMEN

Ribosomes that stall before completing peptide synthesis must be recycled and returned to the cytoplasmic pool. The protein Dom34 and cofactors Hbs1 and Rli1 can dissociate stalled ribosomes in vitro, but the identity of targets in the cell is unknown. Here, we extend ribosome profiling methodology to reveal a high-resolution molecular characterization of Dom34 function in vivo. Dom34 removes stalled ribosomes from truncated mRNAs, but, in contrast, does not generally dissociate ribosomes on coding sequences known to trigger stalling, such as polyproline. We also show that Dom34 targets arrested ribosomes near the ends of 3' UTRs. These ribosomes appear to gain access to the 3' UTR via a mechanism that does not require decoding of the mRNA. These results suggest that ribosomes frequently enter downstream noncoding regions and that Dom34 carries out the important task of rescuing them.


Asunto(s)
Regiones no Traducidas 3' , Proteínas de Ciclo Celular/metabolismo , Endorribonucleasas/metabolismo , Ribosomas/metabolismo , Proteínas de Saccharomyces cerevisiae/metabolismo , Saccharomyces cerevisiae/metabolismo , Diamida/farmacología , Ensayos de Protección de Nucleasas , Biosíntesis de Proteínas , Ribosomas/efectos de los fármacos
2.
Ecotoxicol Environ Saf ; 282: 116682, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-39002380

RESUMEN

The effectiveness, tolerance, and safety of pesticides must be established before their scientific or rational. This study evaluates the field control efficacy of broflanilide, tetraniliprole, and chlorantraniliprole in combating Spodoptera frugiperda in maize crops, as well as the resistance of S. frugiperda to these three diamide pesticides after exposure. By assessing field control efficiency, toxicity, effects on development and reproduction, and detoxification enzyme activity of these diamide pesticides on S. frugiperda, highlights broflanilide's significant insecticidal potential. A highly sensitive and efficient method using QuEChERS/HPLCMS/MS was developed to simultaneously detect residues of these three pesticides on maize. Initial concentrations of broflanilide, tetraniliprole, and chlorantraniliprole ranged from 2.13 to 4.02 mg/kg, with their respective half-lives varying between 1.23 and 1.51 days. Following foliar application, by the time of harvest, the terminal residue concentrations of these pesticides were all under 0.01 mg/kg. Chronic dietary intake risk assessments and cumulative chronic dietary exposure for three pesticides indicated that the general population's terminal residue concentration was within acceptable limits. Not only does this research provide valuable insights into field control efficiency, insecticidal effects, resistance, residues, and risk assessment results of broflanilide, tetraniliprole, and chlorantraniliprole on maize, but additionally, it also paves the way for setting suitable Maximum Residue Limits (MRLs) values based on pre-harvest interval values, rational dosage, and application frequency.


Asunto(s)
Insecticidas , Spodoptera , Zea mays , ortoaminobenzoatos , Spodoptera/efectos de los fármacos , Animales , Insecticidas/toxicidad , Medición de Riesgo , ortoaminobenzoatos/toxicidad , Productos Agrícolas , Residuos de Plaguicidas/toxicidad , Residuos de Plaguicidas/análisis , Diamida/toxicidad , Larva/efectos de los fármacos , Resistencia a los Insecticidas
3.
Pestic Biochem Physiol ; 205: 106140, 2024 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-39477592

RESUMEN

The tomato pinworm, Phthorimaea (=Tuta) absoluta, is considered one of the most destructive and invasive insect pests worldwide, having developed significant resistance to many popular insecticides. In this study, we monitored the field resistance of P. absoluta populations from China to three diamide insecticides: flubendiamide, chlorantraniliprole, and cyantraniliprole. We found that one field population from Wuzhong City (WZ) exhibited high level of resistance to chlorantraniliprole. Using the WZ population and a susceptible reference strain (YN-S), we established a near-isogenic line (WZ-NIL) of P. absoluta with resistance to chlorantraniliprole. This strain also showed substantial cross-resistance to flubendiamide, and cyantraniliprole. Genetic analysis revealed that the inheritance of resistance to chlorantraniliprole in the WZ-NIL strain was autosomal and incompletely dominant. Additionally, the pesticide synergist piperonyl butoxide significantly inhibited chlorantraniliprole resistance by compromising P450 monooxygenase activity, which was significantly higher in the resistant strain. Furthermore, WZ-NIL had significantly prolonged developmental stages, lower pupation rates, reduced female fecundity, and lower egg hatchability than YN-S individuals. The fitness of WZ-NIL relative to YN-S was estimated to be 0.73, indicating significant fitness cost associated with chlorantraniliprole resistance. Rotating chlorantraniliprole with other insecticides that have different modes of action and degradation may be particularly useful for managing chlorantraniliprole resistance in P. absoluta.


Asunto(s)
Resistencia a los Insecticidas , Insecticidas , Mariposas Nocturnas , ortoaminobenzoatos , Animales , ortoaminobenzoatos/farmacología , Insecticidas/farmacología , Resistencia a los Insecticidas/genética , Mariposas Nocturnas/efectos de los fármacos , Mariposas Nocturnas/genética , Pirazoles/farmacología , Butóxido de Piperonilo/farmacología , China , Solanum lycopersicum/efectos de los fármacos , Benzamidas/farmacología , Larva/efectos de los fármacos , Sulfonas/farmacología , Femenino , Diamida/farmacología , Masculino , Pueblos del Este de Asia , Fluorocarburos , Ftalimidas
4.
Chem Biodivers ; 21(7): e202400816, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38676699

RESUMEN

In order to discover new meta-diamide compounds with good activity and novel structure, 15 related compounds were designed and synthesized by the bioisosterism principle with cyproflanilide as the lead compound. The insecticidal activities of these compounds against Plutella xylostella and Tetranychus cinnabarinus were tested, and the results of biological activity test showed that some compounds had more than 90 % insecticidal activity against Plutella xylostella at 1 mg/L and Tetranychus cinnabarinus at 100 mg/L. Especially, N-(2-bromo-6-(difluoromethoxy)-4-(perfluoro propan-2-yl)phenyl)-6-(isonicotinamido)picolinamide against Tetranychus cinnabarinus at 10 mg/L was 100 %, which was better than that of cyproflanilide. Molecular docking studies suggested that N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-6-(4-cyano-2-methylbenzamido)picolinamide had a closely combined with the Plutella xylostella 3RHW (a glutamate-gated chloride channel). This study provides an avenue for designing and synthesizing a new generation of more effective pesticides.


Asunto(s)
Diseño de Fármacos , Insecticidas , Simulación del Acoplamiento Molecular , Mariposas Nocturnas , Piridinas , Tetranychidae , Insecticidas/síntesis química , Insecticidas/química , Insecticidas/farmacología , Animales , Piridinas/química , Piridinas/farmacología , Piridinas/síntesis química , Mariposas Nocturnas/efectos de los fármacos , Relación Estructura-Actividad , Tetranychidae/efectos de los fármacos , Diamida/farmacología , Diamida/química , Diamida/síntesis química , Estructura Molecular
5.
Int J Mol Sci ; 25(4)2024 Feb 19.
Artículo en Inglés | MEDLINE | ID: mdl-38397120

RESUMEN

Diamide insecticides have always been a hot research topic in the field of pesticides. To further discover new compounds with high activity and safety, indane and its analogs were introduced into chlorantraniliprole, and a battery of chlorfenil derivatives, including indane and its analogs, were designed and prepared for biological testing. Their characterization and verification were carried out through nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HRMS). Biological detection showed that all the compounds exhibited good insecticidal activity against Mythimna separata. At 0.8 mg/L, the insecticidal activity of compound 8q against Mythimna separata was 80%, which was slightly better than that of chlorantraniliprole. The results of the structure-activity relationship (SAR) analysis indicated that the indane moiety had a significant effect on insecticidal activity, especially in the R-configuration. The results indicated that chlorantraniliprole derivatives containing indane groups could serve as pilot compounds for the further development of new insecticides.


Asunto(s)
Insecticidas , Mariposas Nocturnas , ortoaminobenzoatos , Animales , Insecticidas/química , Diamida/farmacología , Diseño de Fármacos , Relación Estructura-Actividad , Estructura Molecular
6.
Molecules ; 29(6)2024 Mar 17.
Artículo en Inglés | MEDLINE | ID: mdl-38542973

RESUMEN

The meta-diamide (m-diamide) insecticide, Broflanilide, was characterized by its high efficiency, low toxicity and lack of cross-resistance with traditional GABA receptors. In accordance with the principles of drug molecular design, easily derivable sulfur with diverse bioactivities was introduced while leading with the parent Broflanilide. Twelve novel m-diamide target compounds containing sulfide derivatives were synthesized through exploration guided by the literature. Their structures were confirmed by melting points, 1H NMR, 13C NMR and HRMS. Insecticidal activity assessments revealed that most target compounds A-D exhibited 100% lethality against Plutella xylostella (P. xylostella) and Aphis craccivora Koch (A. craccivora) at 500 mg·L-1. Notably, for P. xylostella, compounds C-2, C-3, C-4 and D-2 demonstrated 60.00-100.00% insecticidal activity even at a concentration as low as 0.625 mg·L-1. As determined by structure-activity relationship (SAR) analysis, compounds with R1 = CH3 and R2 = Br (B-1, C-2 and D-2) and sulfoxide compound C-3 contained 100.00% lethality against A. craccivora at 500 mg·L-1, surpassing the lethality when leading with the parent Broflanilide in terms of efficacy. Consequently, it can be inferred that the sulfoxide compound (C-3) requires further investigation as a potential active molecule for new insecticides. These explorations provide valuable references for future research on the synthesis and insecticidal activities of sulfide-containing m-diamide compounds.


Asunto(s)
Benzamidas , Fluorocarburos , Insecticidas , Mariposas Nocturnas , Plaguicidas , Animales , Estructura Molecular , Diamida/química , Relación Estructura-Actividad , Insecticidas/farmacología , Insecticidas/química , Sulfóxidos
7.
Georgian Med News ; (349): 25-30, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38963196

RESUMEN

Antioxidants are widely used in medicine due to their ability to bind free radicals - active biomolecules that destroy the genetic apparatus of cells and the structure of their membranes, which makes it possible to reduce the intensity of oxidative processes in the body. In a living organism, free radicals are involved in various processes, but their activity is controlled by antioxidants. The purpose of this work was to conduct a series of studies to identify the antioxidant activity of new synthesized compounds of a series of oxalic acid diamides in the brain and liver tissue of white rats in vivo and in vitro experiments, as well as to determine their potential pharmacological properties. The studies were conducted on outbred white male rats, weighing 180-200 g, kept on a normal diet. After autopsy, the brain and liver were isolated, washed with saline, cleared of blood vessels, and homogenized in Tris-HCl buffer (pH-7.4) (in vitro). The research results showed significant antioxidant activity (AOA) of all compounds with varying effectiveness. The most pronounced activity was demonstrated by compound SV-425 in both brain and liver tissues. Compound SV-427 demonstrated the least activity, with levels in brain tissue and liver tissue. In addition, all physicochemical descriptors of the studied compounds comply with Lipinski's rule of five to identify new molecules for the treatment of oxidative stress. From the data obtained, it can be concluded that the studied compounds have antioxidant properties, helping to protect cells from oxidative stress. This is important for the prevention and treatment of diseases associated with increased levels of free radicals.


Asunto(s)
Antioxidantes , Encéfalo , Peroxidación de Lípido , Hígado , Ácido Oxálico , Animales , Encéfalo/metabolismo , Encéfalo/efectos de los fármacos , Hígado/metabolismo , Hígado/efectos de los fármacos , Masculino , Ratas , Antioxidantes/farmacología , Antioxidantes/química , Radicales Libres/metabolismo , Peroxidación de Lípido/efectos de los fármacos , Ácido Oxálico/química , Ácido Oxálico/metabolismo , Ácido Oxálico/farmacología , Diamida/farmacología , Diamida/química , Estrés Oxidativo/efectos de los fármacos , Oxidación-Reducción/efectos de los fármacos
8.
Biochem Biophys Res Commun ; 670: 19-26, 2023 08 30.
Artículo en Inglés | MEDLINE | ID: mdl-37271036

RESUMEN

As a Lepidoptera pest, Spodoptera frugiperda has become one of the major migratory pests causing significant damage to crops. It should prevent and control Spodoptera frugiperda with strong reproductive ability, adaptability, and migration ability, and reduce economic losses as much as possible. Chemical insecticides are mainly used in the emergency control of Spodoptera frugiperda. Diamide insecticide is a kind of pesticide that specifically targets the ryanodine receptor of Lepidopteran pests, which makes it safe, effective, targeted, and low toxicity to mammals. So, it is one of the most concerned and fastest-growing pesticide products after neonicotinoid pesticides. Intracellular Ca2+ concentration can be regulated by ryanodine receptors, and the continuous release of Ca2+ eventually leads to the death of pests and achieve the insecticidal effect. This review introduces in detail diamide insecticides that mainly play roles in stomach toxicity, as well as its specific target-ryanodine receptor, and analyzes how the diamide insecticide acts on the ryanodine receptor and how its mechanism of action can provide a theoretical basis for the rational use of highly effective insecticides and solve the resistance problem. Moreover, we also propose several recommendations for reducing resistance to diamide insecticides, and provide a reference for chemical control and resistance studies of Spodoptera frugiperda, which has broad development prospects in today's increasingly concerned about the ecological environment and advocating green environmental protection.


Asunto(s)
Insecticidas , Animales , Insecticidas/toxicidad , Canal Liberador de Calcio Receptor de Rianodina , Diamida/farmacología , Resistencia a los Insecticidas , Spodoptera , Mamíferos
9.
Mol Biol Rep ; 50(3): 2399-2410, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36586080

RESUMEN

BACKGROUND: Chlorantraniliprole is a diamide insecticide widely used in China over the last 15 years. The fall armyworm (FAW), Spodoptera frugiperda, newly invaded China in 2019. The response of FAW to chlorantraniliprole deserves more attention, in the context of many destructive lepidopteran species are resistant to diamide insecticides and the patent on core chemical of chlorantraniliprole in China expired in August 2022. METHODS AND RESULTS: This study investigated the response profile in larvae under chlorantraniliprole-induced (LC50) stress using methods of bioassay, RNA-Seq and qPCR. We observed growth inhibition and lethal effects in FAW larvae, but at a relatively high LC50 value compared to other several pests. Additionally, under chlorantraniliprole-induced stress, 3309 unigenes were found to be differentially expressed genes. The impacted genes included 137 encoding for detoxification enzymes, 29 encoding for cuticle proteins, and 20 key enzymes involved in the chitin metabolism, which all associated with metabolic resistance. Finally, we obtained the single nucleotide polymorphisms (SNPs) of two RyR genes, which are the target proteins for chlorantraniliprole. We also investigated the causes of the high LC50 value in our FAW, which possibly related to the stabilized 4743 M on SNP frequency of RyR. These findings documented the genetic background of RyR of FAW and indicated that application of chlorantraniliprole has a high risk of controlling FAW in China. CONCLUSION: In brief, our results provide a better understanding of the mechanisms of chlorantraniliprole toxicity and detoxification in FAW, and will aid in monitoring the development of resistant strains for a newly pest to an old insecticide.


Asunto(s)
Insecticidas , Animales , Insecticidas/toxicidad , Spodoptera/genética , Transcriptoma/genética , Diamida/farmacología , Resistencia a los Insecticidas/genética , Larva/genética
10.
Mol Cell ; 58(2): 371-86, 2015 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-25801168

RESUMEN

Covalent histone modifications are highly conserved and play multiple roles in eukaryotic transcription regulation. Here, we mapped 26 histone modifications genome-wide in exponentially growing yeast and during a dramatic transcriptional reprogramming-the response to diamide stress. We extend prior studies showing that steady-state histone modification patterns reflect genomic processes, especially transcription, and display limited combinatorial complexity. Interestingly, during the stress response we document a modest increase in the combinatorial complexity of histone modification space, resulting from roughly 3% of all nucleosomes transiently populating rare histone modification states. Most of these rare histone states result from differences in the kinetics of histone modification that transiently uncouple highly correlated marks, with slow histone methylation changes often lagging behind the more rapid acetylation changes. Explicit analysis of modification dynamics uncovers ordered sequences of events in gene activation and repression. Together, our results provide a comprehensive view of chromatin dynamics during a massive transcriptional upheaval.


Asunto(s)
Cromatina/genética , Diamida/farmacología , Saccharomyces cerevisiae/genética , Cromatina/metabolismo , Ensamble y Desensamble de Cromatina/efectos de los fármacos , Regulación Fúngica de la Expresión Génica , Genoma Fúngico , Histonas/metabolismo , Datos de Secuencia Molecular , Saccharomyces cerevisiae/efectos de los fármacos , Saccharomyces cerevisiae/fisiología , Transcripción Genética
11.
J Toxicol Environ Health A ; 86(15): 518-533, 2023 08 03.
Artículo en Inglés | MEDLINE | ID: mdl-37306479

RESUMEN

The present study examined the acute and chronic toxicity attributed to commercial formulations of the anthranilic diamide insecticides chlorantraniliprole (CHLO) and cyantraniliprole (CYAN) on the neotropical amphibian species Rhinella arenarum, Rhinella fernandezae and Scinax granulatus. The median lethal concentrations obtained after 96 hr exposure (96 hr-LC50) were generally greater than 100 mg/L, except for stage 25 S. Granulatus, which were the most sensitive animals tested with a 96 hr-LC50 value of 46.78 mg/L. In subchronic exposures of R. arenarum, the 21day-LC50 were 151.4 mg/L for CHLO and >160 mg/L for CYAN, the weight gain of the tadpoles during this period not being markedly affected in both cases. Finally, when tadpoles of R. arenarum were exposed to CHLO throughout the metamorphic process, an inverted U-shaped non-monotonic dose-response relationship was observed between exposure concentrations and both % of individuals transiting between stage 39 and 42 and the time required to accomplish this. Data obtained raise the hypothesis of an effect of CHLO on the hypothalamic-pituitary-thyroid (HPT) axis, either directly or through an interaction with the stress-hormone system, as metamorphic progression from stage 39 to S42 occurs under the strict control of thyroid hormones. These observations are important as the anthranilic diamide insecticides are not currently known as endocrine disruptors. Further investigations are needed to clarify the pathways leading to these effects and examine whether environmentally-relevant aquatic concentrations of anthranilic diamides might be impacting amphibian populations in the wild.


Asunto(s)
Insecticidas , Animales , Larva , Insecticidas/toxicidad , Diamida/toxicidad , Anuros
12.
Pestic Biochem Physiol ; 195: 105579, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37666604

RESUMEN

Since 2007, diamide insecticides have been widely used in Korea to control various types of lepidopteran pests including Spodoptera exigua. For nearly a decade, diamide resistance in field populations of S. exigua across 18 localities has been monitored using bioassays. Despite their short history of use, resistance to diamide insecticides has emerged. Based on the LC50 values, some field populations showed a higher level of resistance to chlorantraniliprole, a diamide insecticide, compared to that of the susceptible strain, although regional and temporal variations were observed. To investigate resistance at a molecular level, we examined three mutations (Y4701C, I4790M, and G4946E) in the ryanodine receptor (RyR), which is the primary mechanism underlying diamide insecticide resistance. DNA sequencing showed that only the I4790M mutation was found in most field populations. As resistance levels varied significantly despite the uniform presence of the I4790M mutation, we considered the presence of another resistance factor. Further, the I4790M mutation was also found in S. exigua specimens collected prior to the commercialization of diamide insecticides in Korea as well as in other countries, such as the USA. This finding led us to hypothesize that the I4790M mutation were predisposed in field populations owing to selection factors other than diamide use. For further clarification, we conducted whole-genome sequencing of S. exigua (449.83 Mb) and re-sequencing of 18 individual whole genomes. However, no additional non-synonymous mutations were detected in the RyR-coding region. Therefore, we concluded that the high level of diamide insecticide resistance in Korean S. exigua is not caused by mutations at the target site, RyR, but is attributed to other factors that need to be investigated in future studies.


Asunto(s)
Insecticidas , Canal Liberador de Calcio Receptor de Rianodina , Animales , Spodoptera/genética , Canal Liberador de Calcio Receptor de Rianodina/genética , Museos , Diamida/farmacología , Insecticidas/farmacología
13.
Chem Biodivers ; 20(4): e202300060, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36908182

RESUMEN

In this study, a series of meta-diamide compounds containing ethyl acetate group and their derivatives were designed and synthesized. Their insecticidal activities against Plutella xylostella, Spodoptera frugiperda and Alfalfa sprouts were evaluated. Preliminary bioassays showed that some of the title compounds exhibited excellent insecticidal activities. Especially compound ethyl N-(3-((2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)-N-(4-cyanobenzoyl)glycinate and ethyl N-(3-((2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)-N-(6-fluoronicotinoyl)glycinate showed 100 % mortality at 0.1 mg/L against Plutella xylostella and Spodoptera frugiperda, same to broflanilide. Their LC50 against Plutella xylostella is 0.286 mg/L and 0.0218 mg/L, respectively. Moreover, compound ethyl N-(3-((2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)-N-(6-fluoronicotinoyl)glycinate displayed faster control efficacy than broflanilide at 0.1 mg/L. The results indicated that meta-diamide compounds containing ethyl acetate group could be developed as novel and promising insecticides.


Asunto(s)
Diamida , Insecticidas , Mariposas Nocturnas , Animales , Diamida/análogos & derivados , Diamida/farmacología , Insecticidas/química , Insecticidas/farmacología , Estructura Molecular , Spodoptera , Relación Estructura-Actividad
14.
J Insect Sci ; 23(6)2023 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-38055941

RESUMEN

The nest-scavenging beetle Aethina tumida remains a persistent problem for beekeepers in parts of the Southeast United States, where warm wet soils allow beetle populations to grow rapidly and overwhelm colonies, especially during the summer dearth. Furthermore, small hive beetle infestation prevents beekeepers from easily provisioning colonies with additional pollen or protein feed (patties), preventing holistic management of honey bee health via improved nutrition, and reducing the economic potential of package and nucleus colony rearing in the Southeast. Here, we demonstrate using both in vitro laboratory trials and a small in vivo field trial that the differential specificity of anthranilic diamide insecticides (specifically, chlorantraniliprole) between bees and beetles allows for the control and prevention of small hive beetle infestation in honey bee colonies even when feeding with large patties. Honey bees show orders of magnitude higher tolerance to chlorantraniliprole compared to small hive beetles, opening new avenues for improving bee health including during spring splits and throughout the summer.


Asunto(s)
Abejas , Escarabajos , Insecticidas , ortoaminobenzoatos , Animales , Abejas/efectos de los fármacos , Conducta Animal/efectos de los fármacos , Escarabajos/efectos de los fármacos , Diamida , Himenópteros/efectos de los fármacos , Insecticidas/farmacología , ortoaminobenzoatos/farmacología
15.
Int J Mol Sci ; 24(12)2023 Jun 17.
Artículo en Inglés | MEDLINE | ID: mdl-37373410

RESUMEN

A reaction of acyl chlorides derived from 1,10-phenanthroline-2,9-dicarboxylic acids with piperazine allows the preparation of the corresponding 24-membered macrocycles in good yield. The structural and spectral properties of these new macrocyclic ligands were thoroughly investigated, revealing promising coordination properties towards f-elements (Am, Eu). It was shown that the prepared ligands can be used for selective extraction of Am(III) from alkaline-carbonate media in presence of Eu(III) with an SFAm/Eu up to 40. Their extraction efficiency is higher than calixarene-type extraction of the Am(III) and Eu(III) pair. Composition of macrocycle-metal complex with Eu(III) was investigated by luminescence and UV-vis spectroscopy. The possibility of such ligands to form complexes of L:Eu = 1:2 stoichiometry is revealed.


Asunto(s)
Complejos de Coordinación , Diamida , Modelos Moleculares , Ligandos , Complejos de Coordinación/química
16.
Int J Mol Sci ; 24(6)2023 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-36982643

RESUMEN

Three pyrrolidine-derived phenanthroline diamides were studied as ligands for lutetium trinitrate. The structural features of the complexes have been studied using various spectral methods and X-ray. The presence of halogen atoms in the structure of phenanthroline ligands has a significant impact on both the coordination number of lutetium and the number of solvate water molecules in the internal coordination sphere. The stability constants of complexes with La(NO3)3, Nd(NO3)3, Eu(NO3)3, and Lu(NO3)3 were measured to demonstrate higher efficiency of fluorinated ligands. NMR titration was performed for this ligand, and it was found that complexation with lutetium leads to an approximately 13 ppm shift of the corresponding signal in the 19F NMR spectrum. The possibility of formation of a polymeric oxo-complex of this ligand with lutetium nitrate was demonstrated. Experiments on the liquid-liquid extraction of Am(III) and Ln(III) nitrates were carried out to demonstrate advantageous features of chlorinated and fluorinated pyrrolidine diamides.


Asunto(s)
Flúor , Fenantrolinas , Modelos Moleculares , Fenantrolinas/química , Ligandos , Diamida , Lutecio , Fluoruros , Pirrolidinas , Solventes
17.
Int J Mol Sci ; 24(6)2023 Mar 10.
Artículo en Inglés | MEDLINE | ID: mdl-36982427

RESUMEN

Spodoptera litura is a damaging and notorious insect pest of agricultural crops that has developed resistance to various insecticides. Broflanilide is a novel pesticide with a unique mode of action that displays high efficiency against lepidopterous larvae. We here determined the baseline susceptibility of a laboratory strain of S. litura to broflanilide and 10 other popular insecticides. Furthermore, we measured susceptibility and cross-resistance using three common insecticides in 11 field-collected S. litura populations. Broflanilide caused the highest toxicity among all tested insecticides, with the laboratory strain and all field-collected populations showing high susceptibility. Moreover, no cross-resistance was detected between broflanilide and the other tested insecticides. We subsequently evaluated the sublethal effects of broflanilide and found that treatment with the 25% lethal concentration (LC25) prolonged the development duration in the larvae, reduced the pupation rate and pupae weight, and decreased egg hatchability. Finally, the activities of three detoxifying enzymes were measured in S. litura after treatment with the LC25 dose. The results suggested that enhanced cytochrome P450 monooxygenase (P450) activity could be involved in broflanilide detoxification. Overall, these findings demonstrate the strong toxicity and significant sublethal effects of broflanilide in S. litura and suggest that increased P450 activity may be associated with broflanilide detoxification.


Asunto(s)
Insecticidas , Plaguicidas , Animales , Plaguicidas/farmacología , Insecticidas/toxicidad , Spodoptera , Diamida/farmacología , Larva
18.
Int J Mol Sci ; 24(15)2023 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-37569900

RESUMEN

The spermatozoa have limited antioxidant defences, a high polyunsaturated fatty acids content and the impossibility of synthesizing proteins, thus being susceptible to oxidative stress. High levels of reactive oxygen species (ROS) harm human spermatozoa, promoting oxidative damage to sperm lipids, proteins and DNA, leading to infertility. Coenzyme A (CoA) is a key metabolic integrator in all living cells. Recently, CoA was shown to function as a major cellular antioxidant mediated by a covalent modification of surface-exposed cysteines by CoA (protein CoAlation) under oxidative or metabolic stresses. Here, the profile of protein CoAlation was examined in sperm capacitation and in human spermatozoa treated with different oxidizing agents (hydrogen peroxide, (H2O2), diamide and tert-butyl hydroperoxide (t-BHP). Sperm viability and motility were also investigated. We found that H2O2 and diamide produced the highest levels of protein CoAlation and the greatest reduction of sperm motility without impairing viability. Protein CoAlation levels are regulated by 2-Cys peroxiredoxins (PRDXs). Capacitated spermatozoa showed lower levels of protein CoAlation than non-capacitation cells. This study is the first to demonstrate that PRDXs regulate protein CoAlation, which is part of the antioxidant response of human spermatozoa and participates in the redox regulation associated with sperm capacitation.


Asunto(s)
Antioxidantes , Peróxido de Hidrógeno , Humanos , Masculino , Peróxido de Hidrógeno/farmacología , Peróxido de Hidrógeno/metabolismo , Antioxidantes/farmacología , Antioxidantes/metabolismo , Diamida/metabolismo , Motilidad Espermática , Semen/metabolismo , Estrés Oxidativo , Especies Reactivas de Oxígeno/metabolismo , Espermatozoides/metabolismo , Peroxirredoxinas/metabolismo
19.
Molecules ; 28(2)2023 Jan 12.
Artículo en Inglés | MEDLINE | ID: mdl-36677820

RESUMEN

This work reports the performance of a green corrosion inhibitor with double hydrocarbon chain. The evaluated inhibitor was a dialkyl-diamide from coffee bagasse oil and its electrochemical behavior was evaluated on an API-X52 steel in CO2-saturated brine at 60 °C. The electrochemical behavior was determined by measurements of open circuit potential, polarization resistance, and electrochemical impedance spectroscopy. In addition, the thermodynamic parameters of the corrosion process were obtained in the temperature range from 40 °C to 80 °C. Electrochemical studies showed that the inhibitor is capable of suppressing metal dissolution by up to 99% at 25 ppm. On the other hand, the thermodynamic parameters indicate that when adding the inhibitor, there is a strong increase in both Ea and ΔH° values, and that as time increases, they decrease until reaching similar values to those observed in the absence of the inhibitor. Furthermore, ΔS° values tend to become more negative with immersion time because of the formation of a stable film on the metal surface.


Asunto(s)
Dióxido de Carbono , Café , Corrosión , Diamida
20.
Molecules ; 28(2)2023 Jan 05.
Artículo en Inglés | MEDLINE | ID: mdl-36677619

RESUMEN

Thirty novel diamide compounds combining pyrazolyl and polyfluoro-substituted phenyl groups into alanine or 2-aminobutyric acid skeletons were designed and synthesized with pyflubumide as the lead compound to develop potent and environmentally friendly pesticides. The preliminary bioassay results indicated that the new compounds containing the para-hexa/heptafluoroisopropylphenyl moiety exhibit fungicidal, insecticidal, and acaricidal activities. This is the first time that the para-hexa/heptafluoroisopropylphenyl group is a key fragment of the fungicidal activity of new N-phenyl amide compounds. Most of the target compounds exhibited moderate to good insecticidal activity against Aphis craccivora at a concentration of 400 µg/mL, and some showed moderate activity at a concentration of 200 µg/mL; in particular, compounds I-4, II-a-10, and III-26 displayed higher than 78% lethal rates at 200 µg/mL. Compound II-a-14 exhibited a 61.1% inhibition at 200 µg/mL for Tetranychus cinnabarinus. In addition, some of the target compounds exhibited good insecticidal activities against Plutella xylostella at a concentration of 200 µg/mL; the mortalities of compounds I-1, and II-a-15 were 76.7% and 70.0%, respectively. Preliminary analysis of the structure-activity relationship (SAR) indicated that the insecticidal and acaricidal activities varied significantly depending on the type of substituent and substitution pattern. The fungicidal activity results showed that compounds I-1, II-a-10, II-a-17, and III-26 exhibited good antifungal effects. Enzymatic activity experiments and in vivo efficacy of compound II-a-10 were conducted and discussed.


Asunto(s)
Acaricidas , Fungicidas Industriales , Insecticidas , Mariposas Nocturnas , Animales , Insecticidas/farmacología , Diamida/farmacología , Alanina/farmacología , Diseño de Fármacos , Relación Estructura-Actividad , Fungicidas Industriales/farmacología , Estructura Molecular
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