Synthesis and insecticidal activity of lipophilic amides. Part 3: Influence of chain length and terminal group in N-(2-methylpropyl)-2,4-dienamides

Increasing the alkylene chain length in N-(2-methylpropyl)-ω-phenylalka-2,4-dienamides revealed in addition to the active compounds reported earlier a second peak of activity, but only against mustard beetles, with the tridecadienamide. Similar extension in the methyl-terminated series gave much weaker peaks, at different lengths for the two test species. Results with terminal vinyl compounds were intermediate, and indicated a specific functional role in the lethal process for the terminal unsaturation, with a possible contribution to steric flexibility and physical property optimisation from the longer chains. Synthetic samples of pellitorine and pipercide, natural products to which insecticidal activity has been ascribed, were only very weakly active in the present tests, but compounds with other groups on the ends of chains nearer the optimum length were more active.     

Action of pyrethroids on a nerve-muscle preparation of the clawed frog,Xenopus laevis

The effects of a range of pyrethroids on end-plate potentials and muscle action potentials were studied in the pectoralis nerve-muscle preparation of the clawed frog, Xenopus laevis. The noncyano pyrethroids allethrin, cismethrin, bioresmethrin, and IR-cisphenothrin caused moderate presynaptic repetitive activity only, resulting in the occurrence of multiple end-plate potentials (epps). Trains of repetitive muscle action potentials without presynaptic repetitive activity were observed after the α-ethynyl pyrethroid S-5655 and after the α-cyano pyrethroids cypermethrin, deltamethrin, FCR 1272, and FCR 2769. An intermediate group of pyrethroids consisting of the non-cyano compounds 1R-permethrin, des-cyano-deltamethrin, NAK 1901 and NAK 1963, and the α-cyano pyrethroids cyphenothrin and fenvalerate caused both types of effect. The insecticidally inactive S-enantiomers of permethrin had no effect on the nerve-muscle preparation. Trains of repetitive action potentials in pyrethroid-treated muscle fibers were followed by a depolarizing afterpotential which in general decayed more rapidly for the non-cyano pyrethroids than for the α-cyano pyrethroids. The rate of decay of the depolarizing afterpotential decreased gradually as the temperature was lowered, whereas the pre- and postsynaptic repetitive activity remained largely unaffected over a large temperature range. It is concluded that in muscle membrane like in nerve membrane the pyrethroid-induced repetitive activity is due to a prolongation of the sodium current and that a clear distinction between non-cyano pyrethroids on the one hand and α-cyano compounds on the other cannot be made on the basis of the present results.     

Synthesis and insecticidal activity of new amide derivatives of piperine

The natural lipophilic amides piperine and piperiline were isolated from Piper nigrum L (Piperaceae). Piperine was hydrolysed into piperic acid (85% yield) which was converted into 16 amides (28–89% yield). The contact toxicity of all synthetic amides, and also that of piperine and piperiline, at the dose 10 µg per insect, was evaluated for the Brazilian economically important insects Ascia monuste orseis Latr, Acanthoscelides obtectus Say, Brevicoryne brassicae L, Protopolybia exigua DeSaus and Cornitermes cumulans Kollar. The results demontrated that the insects have different sensivities to the various amides, with mortality ranging from 0 to 97.5% according to the compound and insect species. © 2000 Society of Chemical Industry     

Insecticide screening with isolated nerve preparations for structure-activity relationships

The sciatic nerve-sartorius muscle preparation from the frog, the nerve-muscle preparation from the crayfish, and the abdominal nerve cord preparation from the crayfish have been compared for their sensitivity to various insecticides. The crayfish nerve cord was the most sensitive to insecticides and had a broad spectrum of sensitivity. A method was developed with this preparation to compare a large number of synthetic pyrethroids for their potencies to stimulate and block the nerve which is the primary target site. Both stimulating and blocking actions on the nerve can be assessed with this preparation. Certain pyrethroids are active insecticidally despite their weak nerve action, whereas some other pyrethroids are relatively moderate in killing insects despite their potent nerve action. Thus the new method can be effectively used to establish the true structure-activity relationship of synthetic pyrethroids or any other insecticides acting directly on the nerve.     

The action of pyrethroids in the insect central nervous system. I. Features of molecular structure associated with toxicity to cockroaches and to their giant fibre axons

To investigate relationships between the molecular structure of pyrethroids and their mode of action, toxicities to adult male Periplaneta americana by topical application and injection were compared with toxicities to their giant fibre nerve axons. From the tests against intact insects it was concluded that: (i) although ED₅₀S ranged from 0.04 to 65 μg/insect, each compound was equally toxic, with one exception, when administered by either route; (ii) esters of (1 R)-cis- were more toxic than esters of the corresponding (1 R)-trans-3-substituted-2, 2-dimethylcyclopropanecarboxylic acids; (iii) α-cyano-3-phenoxybenzyl esters were more toxic than the corresponding 3-phenoxybenzyl esters; (iv) changes in the alcoholic component of some compounds (particularly trans-isomers of esters of 5-benzyl-3-furylmethanol and esters of α-cyano-3-phenoxybenzyl alcohol) affected a recovery phase in their ED₅₀/time curves more than changes in the acid component; (v) the amount of recovery was positively correlated with molecular polarity. The concentration required to decrease the amplitude of the action potential of giant fibres by 30% in 1 h ranged from 0.26 μM for the most active compound to 100 μM for the least active. There was no clear relationship between neurotoxicity and toxicity to whole insects and little association between neurotoxicity and features of molecular structure. Neurotoxicity was, however, positively correlated with polarity. Giant fibre axons seem unlikely to be critical sites of action of pyrethroids.     

Toxicity of extracts and isobutyl amides from Piper tuberculatum: potent compounds with potential for the control of the velvetbean caterpillar, Anticarsia gemmatalis

The isobutyl amides pellitorine (compound 1) and 4,5-dihydropiperlonguminine (compound 2) were extracted from the seeds of Piper tuberculatum Jacq. (Piperaceae) in yields of 6.10 and 4.45% respectively. The acute toxicities to the velvetbean caterpillar, Anticarsia gemmatalis (Hübner) (Lepidoptera: Noctuidae), of extracts of seeds, leaves and stems of P. tuberculatum, and of compounds 1 and 2, were evaluated by means of contact bioassays. The extracts caused 80% mortality when doses higher than 800.00 microg insect(-1) of extract of seeds, leaves and stems were administered to the velvetbean caterpillars. Compounds 1 and 2 showed 100% mortality at doses of 200 and 700 microg insect(-1) respectively. The LD(50) and LD(90) values were respectively 31.3 and 104.5 microg insect(-1) for compound 1, and 122.3 and 381.0 microg insect(-1) for compound 2. The potential value of extracts and amides derived from P. tuberculatum as efficient insecticides against velvetbean caterpillars is discussed.     

Isobutyl amides--potent compounds for controlling Diatraea saccharalis

BACKGROUND: A dichloromethane‐methanol extract of the seeds of Piper tuberculatum Jacq. (Piperaceae) and two isobutyl amides, 4,5‐dihydropiperlonguminine (1) and pellitorine (2), which were isolated by chromatographic methods, were assayed for their lethality against the sugarcane borer Diatraea saccharalis F. (Lepidoptera: Pyralidae). RESULTS: Bioassays were carried out with fourth‐instar caterpillars through topical application of test solutions to the dorsal surface of the prothorax, and dose–response correlations were determined. Significant insect mortalities were observed 24, 48 and 72 h after treatment at concentrations of ≥ 100 µg insect^?1. The LD₅₀ and LD₉₀ values for compound 1 were 92.83 and 176.50 µg insect^?1, and for compound 2 they were 91.19 and 184.56 µg insect^?1. CONCLUSION: According to the LD₅₀ and LD₉₀ for compounds 1 and 2, it can be inferred that the values reflect an acute lethal response to both compounds, based on interaction(s) of the toxicants with a primary target or series of targets. Thus, the amides were demonstrated to have potential value in the control of the sugarcane borer. Copyright © 2008 Society of Chemical Industry     

A biochemical approach to potentiate the activity ofBacillus thuringiensis against corn borers

Due to the fact that the persistence ofBacillus thuringiensis (B.t.) is very short in the field as affected by exposure to ultraviolet radiation, some biochemical approaches have been adopted in an attempt to increase potentiation of the pathogen against the two lepidopterous corn borers,Chilo agamemnon andOstrinia nubilalis. These approaches were based on the incorporation of some selected non-toxic chemical compounds with different modes of action with the endotoxin ofB.t. fed to the larvae and thus resulting in its potentiation. Among the compounds tested, some representatives of inorganic salts, organic acids, protein and lipid solubilizing agents, amino acids and amides showed an obvious potentiation to the endotoxin activity against the target insects. Inorganic salts, such as, calcium oxide, calcium carbonate, zinc sulphate and potassium carbonate at 0.1% potentiated the activity of the product Dipel 2X (B.t. var.kurstaki) against the two tested species in varying degrees. With regard to protein solubilzing agents, urea, sodium thioglycollate and EDTA enhanced the potency ofB.t. againstO. nubilalis with a fold increase of 1.4–2.3. The lipid emulsifying agent Tween 80 (0.5%), caused 1.3 fold increase in the potency ofB.t. With respect toC. agamemnon, sodium thioglycollate and EDTA (0.1%) were effective in potentiating the activity ofB.t. with fold increase of 3.1 and 1.2, respectively, while urea caused a decrease in the potency ofB.t as compared with the control. The lipid emulsifying agent Tween 80 (0.5%) caused 1.3 fold increase in the potency ofB.t. The potentiating effect of aromatic compounds is not obvious with respect to the tested insect species. With amino acids and amides, it appears that some of the tested compounds enhanced the potency ofB.t. against the tested insect species but in varying degrees. The mode of action of the tested compounds has been discussed in the light of the results obtained.     

Effect of abamectin on electrophysiological activity in the ventral nerve cord of Periplaneta americana L.: Correlation with symptoms of poisoning and levels of toxicant in vivo

Twenty-four hours after injection of adult male Periplaneta americana with 36 ng [5-³H]abamectin, when symptoms of poisoning were apparent in most individuals, similar levels of radioactivity were found in tissue samples from the ventral nerve cord, metathoracic muscle, fat body and testis of randomly-selected insects. When insects injected with [5-³H]abamectin (36 ng) were separated after 24 h into three groups showing varying symptoms, the level of radioactivity in the ventral nerve cord was found to be significantly greater in partially-paralysed and paralysed groups (4- and 7-fold respectively) than in a treated but non- paralysed group. The mean levels of abamectin in the nerve cords of unaffected, ‘partially-paralysed’ and ‘paralysed’ insects were estimated to be 4, 23 and 37 nM respectively. Extracellular studies of the in-vitro action of abamectin (10 nM and 1 μM) on the spontaneous activity of a picrotoxin-sensitive, partially desheathed, ventral nerve cord preparation of adult male P. americana found the mean response time to be relatively slow (77 and 38 min respectively). In sheathed nerve cords, the mean response time to abamectin (1 μM) was 117 min. In all cases, treatment with abamectin increased the stimulus voltage required to evoke a response. Spontaneous activity was found to be progressively reduced in ventral nerve cord preparations from ‘partially-paralysed’ and ‘paralysed’ insects compared with ‘non-paralysed’ and untreated insects following dissection 24 h after injection of P. americana with unlabelled or labelled abamectin (36 ng), while the stimulus required to evoke activity in the ventral nerve cord showed the reverse trend. These differences in electrophysiological activity could be correlated directly with varying levels of abamectin in the nerve cords of ‘paralysed’ and ‘partially-paralysed’ insects.     

Electrical penetration graph evidence that pymetrozine toxicity to the rice brown planthopper is by inhibition of phloem feeding

BACKGROUND: Pymetrozine is a valuable novel insecticide for control of sucking insects, including the brown planthopper Nilaparvata lugens (Stål), one of the most serious pests on rice. This study was conducted to elucidate the action mechanisms of pymetrozine on the feeding behaviour of the planthopper. RESULTS: The activity test showed that pymetrozine primarily functioned as an antifeedant that caused starvation and death in N. lugens, rather than having neurotoxicity. Pymetrozine‐treated insects died at a significantly slower speed than insects treated with starvation. Electrical penetration graph (EPG) data indicated that pymetrozine significantly increased the duration of non‐probing periods and had a strong inhibition to phloem ingestion. The inhibition was strongly dose dependent, resulting in a complete suppression of the activity in the phloem region when the pymetrozine concentration was increased to 400 mg L^?1. Starvation caused by inhibition of phloem ingestion might be a major toxicity mechanism of pymetrozine. EPG data also showed that pymetrozine had no significant effect on stylet movement and duration of xylem sap ingestion. CONCLUSION: The study revealed that pymetrozine disturbed the feeding behaviour of N. lugens mainly by increasing the non‐probe period and inhibiting phloem ingestion. The inhibition resulted in a slow death similar to starvation. Copyright © 2011 Society of Chemical Industry     

Review A Review of the Mechanisms Involved in the Action of Phosphine as an Insecticide and Phosphine Resistance in Stored-Product Insects

Phosphine gas has been used world-wide for more than four decades as an ideal fumigant for disinfestation of stored grains and other commodities. Its use as a safe fumigant of stored products has become even more important with recent restrictions on the production of the only alternative, methyl bromide. Widespread resistance to phosphine has emerged in several species of stored-product insects in many countries, which in some instances may have caused control failures. Chemically, phosphine is a strong reducing agent and biological redox systems, especially the components of the mitochondrial electron transport chain, are probably the site of its action in insects. The oxidation of phosphine could produce reactive phosphorylating species and interactions of phosphine with biological redox systems have been reported to cause generation of highly reactive oxyradicals. This appears to be the basis of phosphine toxicity to insects, which differs from that of respiratory inhibitors such as hydrogen cyanide. Phosphine-resistant strains of several species of stored-product insects have been reported to absorb very small amounts of the compound compared to their susceptible counterparts. This reduced uptake in resistant insects appears to result from respiratory exclusion of phosphine. The overall mechanism of resistance also involves a detoxification process. Despite the likely involvement of oxyradicals in the insecticidal action of phosphine, the level of anti-oxidant enzymes in resistant insects is apparently not higher than that in their susceptible counterparts. The reduced uptake of the compound might be due either to the presence of a phosphine insensitive target site or to a membrane-based efflux system that excludes phosphine gas in resistant insects. Studies have indicated the oxygen uptake in mitochondrial preparations from susceptible and resistant insects to be equally sensitive to inhibition by phosphine in vitro. The nature of the phosphine-exclusion system in resistant insects has not been fully elucidated. The possibilities of controlling resistant insects with phosphine and prospects for developing new alternative fumigants are also discussed. © 1997 SCI.     

Araucaria angustifolia (Bert.) O. Kuntze induces oxidative and genotoxic damage in larvae of Anticarsia gemmatalis Hübner (Lepidoptera: Erebidae)

Plant-derived products have been considered as an important alternative to common pesticides. Araucaria angustifolia extract (AAE) contains high levels of polyphenols, which are correlated with mortality in defoliating insects. Therefore, this study aimed to evaluate the effects of AAE treatments on A. gemmatalis larvae. Results showed that AAE was able to induce lipid, protein, and DNA damage in the larvae via oxidative stress. AAE treatment did not induce larvae mortality; however, there was an increase in the number of malformed pupae, along with a decrease in the emergence of the insects. These biological effects may be correlated with the polyphenol content of the AAE.     

一些拟青霉菌株对小菜蛾致病性的初步研究

研究了29株拟青霉和1株白僵菌对小菜蛾的致病性。结果表明不同菌株对小菜蛾的致病性有明显差异,其中玫烟色拟青霉,环链拟青霉和球孢白僵菌对小菜蛾感染致死效果最好。另外,分离自虫体的拟青霉菌株对小菜蛾具有较好的致病性,而来自土壤的菌株对小菜蛾无致病性或仅具微弱致病性。环链拟青霉对小菜蛾的致病性与产孢量存在一定的相关性,与地理来源无明显相关性。     

The sensitivity of mitochondrial Mg2+ ATPase to DDT and analogs at different temperatures

Oligomycin-sensitive (O-S) Mg²⁺ ATPase from American cockroach muscle was more sensitive to DDT, TDE, methoxychlor, and DDE at cool temperatures than at warm temperature, thus showing a negative temperature effect. In contrast, inhibition by acaricides dicofol, chlorfenethol, and Plictran shows a positive temperature effect. Oxidative phosphorylation in a mitochondrial preparation from cockroach coxal muscle was reduced by DDT, but the reduction was greater at a higher temperature (32°C) than at a cooler temperature (22°C). In addition, Na⁺K⁺ ATPase from cockroach nerve cord showed a positive temperature effect with DDT. The inhibition by DDT was much less on Na⁺K⁺ ATPase than on O-S Mg²⁺ ATPase. The negative temperature effect by DDT and analogs on O-S Mg²⁺ ATPase parallels toxicity effects on insects and fish as reported by numerous researchers. The results provide further evidence for this energy-regulating enzyme being a critical component in the biological action of DDT.     

Mode of action of β-carboline convulsants on the insect nervous system and their potential as insecticides

Little information is available on the actions of β-carboline convulsants on insect GABA receptors or their potential as insecticides. Accordingly, two compounds (3-ethoxy-β-carboline, 3-EBC; dimethoxy-β-carboline-3-methyl ester, DMCM) were studied for their effects on Drosophila melanogaster larval neuron discharge and also in lethality bioassays on adult female D. melanogaster and adult male Blattella germanica. Recordings of nerve spiking in the isolated larval central nervous system showed that 3-EBC and DMCM inhibited nerve discharge, and this inhibitory effect was not additive with that of GABA, confirming that the inhibition was expressed through an action on the GABA receptor. Nerve blockage induced by β-carbolines could not be reversed by picrotoxinin, indicating that there may exist some overlap or negative allosteric coupling between the picrotoxinin and β-carboline binding sites. DMCM and 3-EBC effectively antagonized the effects of exogenously applied GABA in nerve preparations from insecticide-susceptible larvae. In contrast, preparations from the rdl strain of D. melanogaster, which possesses a GABA receptor that is highly resistant to cyclodienes and related convulsants, were less sensitive to the GABA antagonist effect of DMCM. Neither of the β-carbolines produced any appreciable mortality in insects, even when synergized with piperonyl butoxide or S,S,S-tributyl phosphorotrithioate, The toxicity of the β-carbolines is probably limited by their relatively weak effects on the GABA receptor and perhaps also by pharmacokinetic factors. These considerations, coupled with the cross-resistance observed in cyclodiene-resistant insects, suggest that the currently available β-carbolines are not viable as lead compounds for insecticide screening efforts. © 1997 SCI.     

苦楝中几种杀虫有效成分对菜青虫和亚洲玉米螟的生物活性

采用生物活性追踪法,从苦楝根皮、树皮和果实中分离出多种四环三萜类杀虫有效成分。这些成分对菜青虫和亚洲玉米螟均表现出明显的拒食活性,川楝素对菜肯虫还有明显的胃毒活性。从苦楝中分离出的几种非四环三萜类物质对昆虫的生物活性均较低,仅表现出一定的拒食活性。另外对几种三萜衍生物的生物活性进行了测定与比较。     

Actions of azadirachtin,a plant allelochemical,against insects

Investigations of the antifeedant mode of action of azadirachtin and four synthetic analogues, 22,23-dihydroazadirachtin, 3-tigloylazadirachtol, 11-methoxydihydroazadirachtin and 22,23-bromoethoxydihydroazadirachtin have revealed that both polyphagous and oligophagous insects are behaviourally responsive to azadirachtin, with the most responsive species being able to differentiate extremely small changes in the parent molecule. In Lepidoptera the antifeedant response is correlated also with increased neural activity of the chemoreceptors. When locusts are treated on crop plants, the antifeedant and physiological actions of azadirachtin and analogues work in concert and result in feeding deterrence, growth and moulting aberrations and mortality with the same order of potency as for antifeedancy. Specific binding studies using [³H]dihydroazadirachtin carried out on locust testes and Spodoptera Sf9 cells have shown that the competitive binding of the different analogues of azadirachtin to these binding sites occurs in a similar order of potency to that found with antifeedant and IGR bioassays. This suggests a causal link between specific binding to membrane proteins and the ability of the molecule to exert biological effects. © 1998 Society of Chemical Industry     

Characteristics of the transmission of Sumatra disease of cloves by tube-building cercopoids, Hindola spp.

Repeated transmission tests showed that the tube-building cercopoids Hindolafulva (in Sumatra) and H. striata (in Java) were natural vectors of Sumatra disease of cloves, caused by Pseudomonas syzygii . In tests on experimental transmission of P , syzygii, H , striata collected from a disease-free area acquired bacteria within 4 h of access to infected plants and transmitted them within 4 h of access to healthy test plants. Transmission was persistent and commenced within 24 h of acquisition feeding, but there was evidence for a short latent period between acquisition and transmission of bacteria. After acquisition feeding, P . syzygii was isolated from 67% of insects that transmitted the disease and also from 3% of those that did not. Times to death of test plants following first exposure to both naturally and experimentally infective insects showed log-normal distributions with similar slopes. Younger (1-year) seedlings died slightly sooner (median response time = 200 days) than older (2- to 3-year) test plants (median response time = 280 days). The bacterial content of test plants was positively correlated with time to death.     

丛枝菌根真菌和甜菜夜蛾的相互作用

为探索丛枝菌根(arbuscular mycorrhiza,AM)真菌与植食性昆虫的相互作用,将摩西管柄囊霉(Funneliformis mosseae BEG167,Fm)、根内球囊霉(Glomus intraradices BEG141,Gi)和地表球囊霉(Glomus versiforme Berch,Gv)3种AM真菌以及甜菜夜蛾Spodoptera exigua分别接种至花生和番茄上,通过测定AM真菌的侵染定殖和甜菜夜蛾的生长发育指标分析AM真菌与甜菜夜蛾的相互作用。结果显示,甜菜夜蛾取食菌根花生植株后,Fm、Gv和Gi的侵染率和泡囊数均有增加,侵染率分别是未取食的1.15、1.10和1.11倍,而Fm的泡囊数增加最显著,是未取食的1.27倍。在菌根番茄植株上,Fm和Gv的侵染率显著增加,分别是未取食的1.24倍和1.94倍,Fm、Gv和Gi的泡囊数均显著增加,分别是未取食的1.50、1.98和1.42倍。甜菜夜蛾取食菌根花生和菌根番茄植株后,幼虫存活率下降,幼虫历期和蛹期明显延长;Fm对其影响最显著,甜菜夜蛾在花生上的存活率、幼虫历期和蛹期分别为26.67%、26.78 d和10.67 d,在番茄上分别为35.52%、24.33 d和10.39 d,与取食非菌根植株处理差异显著。表明甜菜夜蛾能在一定程度上促进AM真菌的侵染和定殖,而AM真菌能抑制甜菜夜蛾的生长和发育,但其影响因AM真菌种类而不同。     

Resistance management strategies in malaria vector mosquito control. A large-scale field trial in Southern Mexico

A resistance management programme comparing rotations, mosaics and single use of insecticides for residual house-spraying against the insect vectors of malaria is being carried out in Southern Mexico. The area was chosen because of its prior history of insecticide use, relatively sedentary vector, and physical features of the area which limit inward migration of insects to the study area. A high level of resistance to DDT and low levels of organophosphorus (OP), carbamate and pyrethroid resistance were detected by WHO discriminating-dose assays in field populations of Anopheles albimanus in the pre-spray period in the region where this resistance management project is being undertaken. After the first year of spraying, resistance, as measured by a discriminating-dose assay, was still at a high level for DDT and had risen for all the other insecticides. Biochemical assays showed that DDT resistance was primarily caused by elevated levels of glutathione S-transferase (GST) activity leading to increased rates of metabolism of DDT to DDE. The numbers of individuals with elevated GST and DDT resistance were well correlated, suggesting that this is the only major DDT resistance mechanism in this population. The carbamate resistance in this population was conferred by an altered acetylcholinesterase (AChE) mechanism. The level of resistance in bioassays correlated well with the frequency of individuals homozygous for the altered AChE allele. This suggests that the level of resistance conferred by this mechanism in its heterozygous state is below the level of detection of the bioassay. The low levels of OP and pyrethroid resistance could be conferred by either the elevated esterase or monooxygenase enzymes. The esterases, however, are elevated only with p-nitrophenyl acetate (PNPA), and are unlikely to be causing broad-spectrum OP resistance. The altered AChE mechanism may also be contributing to the OP but not the pyrethroid resistance. There were significant differences in some resistance gene frequencies for insects obtained by different indoor and outdoor trapping methods. To determine whether the different sampling methods were effectively sampling the same interbreeding population, RAPD analysis of insects obtained by different collection methods in different villages was undertaken. There was no observed variability in the RAPD patterns for the different mosquito samples with a number of primers. ©1997 SCI