Molluscicidal and anti-feedant activities of diterpenes from Euphorbia paralias L

Nine known diterpene polyesters of segetanes, jatrophenes and paralianes have been isolated from the aerial parts of Euphorbia paralias L. The molluscicidal activity of isolated compounds was evaluated on Biomphalaria alexandrina (Ehrenberg). Paraliane diterpene, (2S,3S,4R,5R,6R,8R,12S,13S,14R,15R)-5,8,14-triacetoxy-3-benzoyloxy-15- hydroxy-9-oxo-paraliane, was the most potent compound against the snail. Anti-feedant activity was tested by a conventional leaf disc method against third-instar larvae of Spodoptera littoralis (Boisd). Jatrophene diterpene, (2R,3R,4S,5R,7S,8R,13R,15R)-2,3,5,7,15-pentaacetoxy-8-angeloyloxy-14,15- dioxojatropha-6(17)-11E-diene, had the highest anti-feedant activity among the compounds tested.     

Comparison of anti-feedant and insecticidal activity of nimbin and salannin photo-oxidation products with neem (Azadirachta indica) limonoids

Photo-oxidation of the neem limonoids nimbin and salannin with UV light in the presence of oxygen gives two isomeric lactone products per limonoid, nimbinolide and isonimbinolide, and salanninolide and isosalanninolide, respectively. When compared in insect tests with the important limonoids of neem seeds, azadirachtin, nimbin and salannin, isonimbinolide and isosalanninolide show activity greater than that of nimbin or salannin and in some respects show activity approaching that of azadirachtin. The photo-oxidation products were tested for anti-feedant activity and toxicity against larvae of three species of Lepidoptera, Spodoptera littoralis (Boisd), Spodoptera frugiperda (FE Smith) and Helicoverpa armigera (Hübner) and nymphs of the locusts Schistocerca gregaria (Forsk?l) and Locusta migratoria (L).     

黄花蒿粗提物对几种害虫拒食性的初步研究

以黄花镐为原料进行浸提，经生物活性测定，结果表明黄花蒿Artenisia annua L.粗提物对供试的6种害虫均具有拒食性。其中对黑翅土白蚁Odontotermes formosanus Shiraki、赤拟谷盗Thibolium castaneum Herbst、谷蠹Rhizopertha dominica Fabricius拒食性极强，对棉蚜Aphis gossypii Glover、棉红蜘蛛Tetranychus urticae Koch及豇豆荚螟Etiella zinckenella Treitschke 也具有较强的巨食性。使用黄花蒿粗提物时，以稀释500倍和800倍效果最好，处理与对照之间有极显著差异。     

Foliar Persistence and Residual Activity of Tebufenozide Against Spruce Budworm Larvae

A field study was conducted to investigate the persistence of tebufenozide in white spruce foliage. An aqueous suspension concentrate formulation, RH-5992 2F, was sprayed over single trees at three dosage rates, 35, 70 and 140 g of the active ingredient (AI), in 2·0 litre ha⁻¹, using ground application equipment. Foliage was collected at different intervals of time up to 64 days after treatment and tebufenozide residues were measured by high-performance liquid chromatography. Foliage was also fed to laboratory-reared 4th- and 6th-instar spruce budworm (Choristoneura fumiferana Clemens). The data indicated that tebufenozide residues in foliage declined with time according to first-order kinetics. The average rate-constant and half-life of disappearance (DT₅₀) were 0·0340 and 20·45 days, respectively. Larval mortality declined gradually, corresponding to the residues, but was still appreciable (49 to 70%) when the larvae were fed with foliage collected 64 days after treatment. The amount of foliage consumed by the larvae decreased when foliar residues of tebufenozide increased, thus indicating anti-feedant activity of the chemical. The LD₅₀ values for both instars were similar and averagedc.25 ng per insect, but the LD₉₀ values were significantly lower for 4th-instar than for 6th-instar, at 63·6 and 96·1 ng per insect respectively. This implies that, theoretically, at a foliar concentration of 1·0 μg tebufenozide g⁻¹ foliage (fresh wt), the spruce budworm larva needs to consume 65 to 100 mg of foliage in 10 days to cause mortality in about 90% of a population of the insect.     

Toxicity and biochemical study of two insect growth regulators, buprofezin and pyriproxyfen, on cotton leafworm Spodoptera littoralis

Lethal and sublethal effects of two insect growth regulators (IGRs) buprofezin and pyriproxyfen were evaluated on larvae of cotton leafworm Spodoptera littoralis. Activity of chitinase and polyphenol oxidase (PPO) in surviving larvae after treatment was carried out in order to investigate the biochemical influences of these compounds. The compounds were low toxic against the larvae at 0.05, 0.1, 0.25, 0.5, and 1.0-fold of the field application rate. However, the overall mortalities within 6 days of feeding at 2.0-fold were 46.67% and 100% for buprofezin and pyriproxyfen, respectively. Larval weight gain was considerably decreased as concentration increased. Pyriproxyfen showed high antifeedant activity in a concentration-dependent manner, and larvae stopped to eat from the third day with high dose. Conversely, buprofezin did not significantly show antifeedant except with high concentration (3000 mg (a.i.)/kg diet) that gave 80.68%. The high doses of both compounds showed adverse effects on pupae, and emergence of adults. Buprofezin at the recommended dose (1500 mg (a.i.)/kg diet) caused 93.33% pupation and 53.33% emergence of adults. Otherwise, pyriproxyfen caused 21.33% pupation and zere emergence of adults at the recommended dose (75 mg (a.i.)/kg diet) compared to 100% pupation, and 96.30% emergence of adults in the control. Both compounds varied in their influences on chitinase and PPO activity, and these enzymes could have relation with toxicity of buprofezin and pyriproxyfen against S. littoralis larvae.     

The importance of nerve terminal depolarization in pyrethroid poisoning of insects

The effects of several pyrethroids and DDT were examined on neuromuscular preparations from larvae of Musca domestica, Culex quinquefasciatus, Anopheles stephensi, and Trichoplusia ni, in order to determine the importance of the type I effect (repetitive firing) and the type II effect (increased miniature excitatory postsynaptic potential (mepsp) rate, indicating nerve terminal depolarization) in the poisoning process. α-Cyano pyrethroids were very potent in increasing mepsp rate, and although DDT and non-α-cyano compounds were more potent at inducing repetitive firing, all these compounds increased mepsp rate at higher concentrations. A variety of evidence showed that the mepsp rate-increasing activity could be an important factor in toxicity: among all of the compounds, there was a positive correlation between toxicity and mepsp rate-increasing activity; mepsp rate-increasing activity had a negative temperature dependence; nerves of kdr larvae in vitro were resistant to the mepsp rate-increasing activity, commensurate with resistance level; and finally, increased mepsp rate and neuromuscular block were observed in poisoned insects, associated with paralysis. Among type I compounds, repetitive firing activity was correlated negatively with toxicity, but positively with knockdown activity.     

天然杀线虫先导化合物Waltherione A类似物的合成及杀线虫活性

为了找出天然杀线虫先导生物碱Waltherione A的关键药效基团并简化其结构,以2,3-二甲氧基苯甲醛和3,4-二甲氧基苯甲醛为原料,经过分子内傅克烷基化反应形成苯并七元氧桥环,并用不同的取代基与桥环相连,合成了12个Waltherione A类似物,其中8个化合物未见文献报道,所有目标化合物的结构均通过核磁共振氢...     

炔类化合物对亚洲玉米螟拒食活性和电生理反应

利用饲料柱法测定了人工合成的 9个共轭二炔和 3个单炔类化合物对亚洲玉米螟 Ostrinia furnacalis(Guene'e) 5龄幼虫的拒食活性 ,并利用顶端记录技术 ,诱发该虫栓锥感受器感受细胞的电位脉冲反应。结果表明 :受试的炔类化合物对亚洲玉米螟幼虫具有不同程度的拒食活性 ,特别是化合物 2 (6,6-二甲基-2,4-庚二炔-1-醇、化合物 3(2,4-己二炔-1,6-二醇 )、化合物 9(1-苯基-2 ,4-己二炔 )和化合物 11(3-溴-2-丙炔-1-醇 ) ,实验剂量为 500μg/g饲料时 ,2 4 h非选择性拒食率在 80%左右。电生理测定结果表明 :浓度为 1mg/mL时 ,该系列化合物刺激中栓锥感受器能诱发感受细胞发放不同频率的脉冲和振幅 ,脉冲频率在 8.30～31.00imp/s,振幅在 400～1000μV之间。刺激侧栓锥感受器 ,也能诱发感受细胞发放不同频率的脉冲 ,脉冲频率在 6.00～ 15.66imp/s之间。将化合物诱发中栓锥感受细胞电位脉冲频率与生测拒食活性进行比较 ,发现二者存在一定程度的相关性。在剂量 -发放频率测试中 ,测得化合物 9诱发栓锥感受器脉冲频率具有浓度依赖性。     

两种化合物对菜粉蝶幼虫超氧化物歧化酶的影响

室内测试了菜粉蝶 Pieris rapae 4 龄幼虫超氧化物歧化酶的活性，并就 α -三噻吩（ α -terthienyl）和化合物5［1-苯基-4-（3，4-亚甲基 二氧）苯基-丁二炔］两种化合物对其产生的影响进行了比较研究。结果表明，近紫外光照 （300～400 nm）可增强对幼虫超氧化物歧化酶活体活力( in vivo )和离体活力( in vitro )。经光敏化合物处理后，在紫外光照下，超氧化物歧化酶活体活力基本不受化合物 5的影响，但能被 α -三噻吩抑制；离体情况下，无论光照与否，化 合物5均不影响其活力， α -三噻吩在低剂量下有抑制作用，而在高剂量下则可使其活力 增强，显示了不同的剂量反应关系。表明无论在离体还是活体的情况下，幼虫对 α -三噻吩的光敏性优于化合物5。对两种化合物光敏作用的可能机理进行 了探讨。     

The sub-lethal activity of amidines on insects and acarids

A number of straight-chain and cyclic amidines at sub-lethal concentrations elicit a variety of responses from target organisms, usually expressed as a disruption of normal behaviour, leading to reduced feeding of lepidopterous larvae and tick detachment, or reduced fecundity. These effects are particularly evident in Acarina and Lepidoptera, but can also be seen in members of other insect orders. In some previously unpublished experiments, it was demonstrated that some of these compounds act as ‘locomotor stimulants’ to decrease the feeding of lepidopterous larvae. This type of activity probably results from the interaction of these compounds with aminergic in the case of some compounds identified as octopaminergic neurotransmitter/neuromodulator systems in the target organisms. It is not always clear, however, to what extent this type of activity contributes to the control of pests in the field situation.     

Effect of uneven application of azadirachtin on reproductive and anti-feedant behaviour of Rhyzopertha dominica (Coleoptera: Bostrichidae)

The effects of uneven application of an azadirachtin-enriched neem extract to wheat grain on the reproduction and feeding behaviour in Rhyzopertha dominica (F) were investigated. The evenness of distribution amongst individual wheat grains during grain treatment was not important in ensuring its effectiveness as an anti-feedant or as an insect growth regulator, provided that, overall, the grain was treated with an effective level of azadirachtin. The effect of azadirachtin on reproduction was not improved when the diluent application rates were increased from 0.5 ml kg⁻¹ to 5 ml kg⁻¹. Treating 10% of the grain was shown to provide the same level of protection as treating 100% of the grain. The anti-feedant effect of azadirachtin on the beetle was also unaffected by unevenness of treatment, provided that 50% of the grain was treated. The fact that azadirachtin remains effective even when application to grain is uneven may be advantageous in field situations where uniform distribution of insecticides is difficult to achieve. © 1999 Society of Chemical Industry     

透骨草杀虫活性成分分离鉴定及其生物活性研究

采用柱层析分离、高效液相色谱切分和生物活性追踪法,从透骨草Phryma leptostachya L.石油醚提取物中分离出2个具有杀虫活性的化合物(B1和B2),采用质谱、核磁共振氢谱和碳谱,并结合相关文献对其结构进行鉴定,发现其分别为双氧木脂素A 和E。首次以粘虫Mythimna separata、槐尺蠖Semiothisa cinerearia、小菜蛾Plutella xylostella、小地老虎Agrotis ypsilon和家蝇Musca domestica为试虫,测定了这2个化合物的杀虫活性。结果表明:化合物 B1和B2 对3龄粘虫24 h的胃毒致死中浓度(LC50值)分别为34.9和52.8 μg/mL,24 h触杀致死中量(LD50值)分别为0.09和0.26 μg/头;对3龄槐尺蠖24 h的胃毒LC50值分别为66.1和1 675 μg/mL,触杀LD50值分别为0.049和1.33 μg/头;对家蝇成虫24 h的胃毒LC50值分别为39.2和969 μg/mL,触杀LD50值分别为0.047和1.12 μg/头。     

Structure–activity relationships of eugenol derivatives against Aedes aegypti (Diptera: Culicidae) larvae

BACKGROUND: Dengue fever is a severe public health problem for several countries. In order to find effective larvicides to aid control programs, the structure‐activity relationships of eugenol derivatives against Aedes aegypti (Diptera: Culicidae) larvae were evaluated. Additionally, the composition and larvicidal activity of Syzygium aromaticum essential oil was assessed. RESULTS: Four compounds representing 99.05% of S. aromaticum essential oil have been identified. The essential oil was active against Ae. aegypti larvae (LC₅₀ = 62.3 and 77.0 ppm, field‐collected and Rockefeller larvae respectively). The larvicidal activity of eugenol, the major compound of the essential oil, was further evaluated (LC₅₀ = 93.3 and 71.9 ppm, field‐collected and Rockefeller larvae respectively). The larvicidal activity and structure‐activity relationships of synthetic derivatives of eugenol were also assessed. The larvicidal activity of the derivatives varied between 62.3 and 1614.9 ppm. Oxidation of eugenol allylic bond to a primary alcohol and removal of the phenolic proton resulted in decreased potency. However, oxidation of the same double bond in 1‐benzoate‐2‐methoxy‐4‐(2‐propen‐1‐yl)‐phenol resulted in increased potency. CONCLUSION: Structural characteristics were identified that may contribute to the understanding of the larvicidal activity of phenylpropanoids. The present approach may help future work in the search for larvicidal compounds. Copyright © 2012 Society of Chemical Industry     

Synthesis and insecticidal activities of novel derivatives of podophyllotoxin: Part XII

In order to find the biorational pesticides, eight novel 4β-substituted phenoxyaniline derivatives of podophyllotoxin have been synthesized with significant stereoselectivity and improved yields by employing the BF₃·Et₂O/NaI reagent system and evaluated for their antifeedant effect against 5th instar larvae of Pieris rapae and effect on the development of 5th instar larvae of P. rapae as well as for insecticidal activity against P. rapae. The antifeedant activities showed that these compounds exhibited less potent than podophyllotoxin. Though these derivatives showed less potent antifeedant activities than podophyllotoxin, they acted as growth development inhibitor to 5th instar larvae of P. rapae, which were found that the animals treated with podophyllotoxin and its derivatives showed moulting disturbances and/or deformities. Also, the insecticidal activity results show that all of these derivatives of PPT showed delayed insecticidal activity, which differs from traditional neurotoxic insecticides. Among them, compounds possessing a 4β-phenoxyaniline moiety substituted (CO₂C₂H₅, Cl and OH) at para position exhibited greater insecticidal activity against P. rapae than podophyllotoxin.     

含酰腙结构的新型吡唑酰胺衍生物对小菜蛾的生物活性

采用浸虫法、夹毒叶片法和叶碟法分别测定了13个含酰腙结构的新型吡唑酰胺衍生物对小菜蛾3龄幼虫的触杀、胃毒和拒食活性。结果表明:该类化合物对小菜蛾3龄幼虫具有较高的胃毒和拒食活性,其中苯环上含有氯原子、且酰腙一端的取代基含有杂原子且体积较小的化合物 H7的胃毒和拒食活性最好,明显高于对照药剂毒死蜱。H7 72 h胃毒作用LC50值为0.6 mg/L(毒死蜱的LC50值为7.4 mg/L);有10个化合物的拒食活性高于毒死蜱,其中 H7 48 h的拒食中浓度(AFC50) 最低,为0.6 mg/L,明显低于毒死蜱(AFC50=6.5 mg/L)。供试化合物对小菜蛾3龄幼虫均无触杀活性。     

两种海洋真菌混合发酵的次级代谢产物及杀虫活性研究

为了研究海洋真菌哈茨木霉Trichoderma harzianum ABC19819和短柄青霉菌Penicillium Brefeldianum ABC190807混合发酵产生的次级代谢产物,利用硅胶柱色谱、Sephadex LH-20凝胶柱色谱和薄层色谱等多种分离纯化手段对混合发酵所产生的次级代谢产物进行分离纯化,结...     

杠柳新苷类化合物对东方黏虫的杀虫活性及对中肠细胞刷状缘膜囊泡3种特征酶活性的影响

为了研究和阐明杠柳新苷类杀虫活性化合物对东方黏虫的杀虫活性及作用靶标,采用载毒叶片饲喂法测定比较了6个杠柳新苷类化合物 (PSA、PSD、PSE、PSF、PSP和PST) 对3龄东方黏虫Mythimna separata Walker幼虫的毒力;应用MgCl₂沉淀差速离心法制备东方黏虫中肠细胞刷状缘膜囊泡 (BBMV) 基础上,测定了6个化合物对东方黏虫幼虫中肠细胞BBMV中3种特征酶——氨肽酶、碱性磷酸酶及V-ATP酶活性的影响。结果表明:杠柳新苷P (PSP) 和T (PST) 对3龄东方黏虫幼虫表现出较高的杀虫活性,其24 h的致死中浓度(LC₅₀值) 分别为1.60和1.23 mg/mL,杠柳新苷A (PSA)、D (PSD) 和F (PSF) 仅表现出微弱的杀虫活性 (LC₅₀ > 20 mg/mL),而杠柳新苷E (PSE)则无明显杀虫活性。酶活性测定结果表明,6个杠柳新苷类化合物对氨肽酶和碱性磷酸酶活性均没有明显的抑制作用,而高杀虫活性化合物PSP和PST则可浓度依赖地抑制V-ATP酶活性。推测杠柳新苷类杀虫活性化合物的作用靶标与V-ATP酶有密切关系。     

5,7,4-三羟基黄酮等生物源化合物对菜青虫幼虫生长发育的影响

为了研究生物源化合物对菜青虫幼虫Pieris rapae（L.）生长发育的影响,选用5,7,4＇-三羟基黄酮、槲皮素、芦丁、5-甲氧基水杨酸和曲酸5种化合物,以触杀和摄食毒力法进行了生物活性测定.结果表明,5,7,4＇-三羟基黄酮和槲皮素对菜青虫幼虫生长发育具有明显的影响,浸渍法处理后72 h,两种化合物对试虫致死LC50值分别为0.226和0.951g/L;叶片药膜法处理后72 h,LC50值分别为0.062和2.420 g/L.结果还表明,采用叶片药膜法,当5,7,4＇-三羟基黄酮的浓度高于0.200g/L时,所有试虫均不能正常化蛹;采用浸渍法,用5,7,4＇-三羟基黄酮、槲皮素、芦丁、5-甲氧基水杨酸和曲酸处理的菜青虫5龄幼虫体重与对照相比增长量明显降低.离体试验结果显示,5,7,4＇-三羟基黄酮和槲皮素对菜青虫酚氧化酶（phenoloxidase,EC.1.14.18.1）具有明显的抑制作用,抑制中浓度（IC50）分别为25.65和43.94mg/L.     

4-β-O-酰基鬼臼毒素和4-β-O-烷基鬼臼毒素 的合成及其拒食活性

为研究鬼臼毒素类化合物结构与杀虫活性的关系,合成了4个4-β-O-酰基鬼臼毒素和3个 4-β-O-烷基鬼臼毒素类化合物,其中5个化合物未见文献报道,其结构经MS、1H NMR和元素分析确证。采用小叶碟添加法测试了所合成化合物对3龄粘虫Mythimna separate幼虫24 h和 48 h的拒食活性,结果表明:4-β-O-烷基鬼臼毒素类化合物的活性相对高于酰基化产物和对照鬼臼毒素(PPT)和脱氧鬼臼毒素(DPPT)。其中,4-β-O-甲基鬼臼毒素48 h的活性最高,其拒食中浓度(AFC50)为144.6 mg/L,是DPPT的4.3倍。酰基化鬼臼毒素类化合物的活性相对较低。     

A note on the effects of fluorine substituents on the biological activity and environmental chemistry of benzoylphenylureas

Halogen-substituted benzoyl ureas have been shown to possess interesting activity against insect larvae, preventing their development by interfering with the formation of cuticular tissue. Certain fluorinated compounds are particularly active. Activity can be related to certain characteristics, notably the spatial structure of the compound, so that those of optimum activity can be predicted.