The antifeedant effect of some new withanolides on three insect species,spodoptera littoralis,epilachna varivestis andtribolium castaneum

The antifeedant effect of several new withanolides on larvae ofSpodoptera littoralis, Epilachna varivestis andTribolium castaneum was investigated. 2,3-Dihydrowithanolide E (II) was an antifeedant forS. littoralis andE. varivestis; nicalbin A (XIV), and a mixture of withanicandrin (IX) and daturalactone A (X), were active against E. varivestis andT. castaneum. Some activity was shown by 6β,14α,17β,20α_F-tetrahydroxy-1-oxowitha-2,4,24-trienolide (V) againstS. littoralis; 4β,5β-epoxy-6α,14α,17β,20α_F-tetrahydroxy-l-oxowitha-2,24-dienolide (VII) againstE. varivestis andT. castaneum; 5α,6α,-epoxy-14α,17β,20α_F-trihydroxy-1-oxowitha-2,24-dienolide (VI) againstE. varivestis; and nicalbin B (XV) againstT. castaneum.     

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.     

Distribution of the chemotypes ofWithania somnifera in some areas of Israel: Feeding studies withSpodoptera littoralis larvae and chemical examination of withanolide content

The geographical distribution of the chemotypes ofWithania somnifera Dun. (Solanaceae) in Israel was re-investigated. In the distribution area of chemotype II (major steroidal constituent, withanolide D), plants of chemotype III (major steroidal constituent, withanolide E) were also found. The antifeedant properties forSpodoptera littoralis larvae of leaves ofW. somnifera populations belonging to chemotype III are due to the presence of withanolide E and may be used, as a supplement to chemical analysis, to differentiate between chemotype III and other chemotypes ofW. somnifera.     

苍耳倍半萜内酯和博落回生物碱对三种蔬菜害虫的活性比较

为探讨苍耳（Xanthium sibiricum）倍半萜内酯分离物L-Ⅱ (主要成分为4β,5β-环氧苍耳素-1α,4α-内过氧化物) 的活性大小,将其与博落回（Macleaya cordata）总生物碱提取物MacSC （主要成分为血根碱和白屈菜红碱）的活性进行了比较研究。结果显示,两种测试物对试虫均表现较高活性,其中,苍耳倍半萜内酯分离物L-Ⅱ对小菜蛾（Plutella xylostella ）4龄幼虫的选择性拒食中浓度（AFC₅₀）为23.6 mg/L,活性强于博落回生物碱提取物MacSC（111.8 mg/L）;在测试浓度为10 mg/mL时,L-Ⅱ处理组的小菜蛾4龄幼虫仅有4.30%发育为成虫,是对照的6.12%,小菜蛾蛹的羽化率为对照的12.05%,而MacSC的影响相对较低,两值分别为对照的33.89%和56.23%; 在上述测试浓度,L-Ⅱ对桃蚜 （Myzus persicae）和萝卜蚜（Lipaphis erysimi）均有较强的忌避作用,24 h忌避率分别为72.03%和74.47%,而MacSC对桃蚜的忌较效果较低（55.50%）,对萝卜蚜无忌避活性。说明苍耳倍半萜内酯分离物L-Ⅱ对几种试虫的拒食、忌避和生长发育抑制活性均高于博落回总生物碱提取物MacSC。     

Response ofSpodoptera littoralis (Boisd.) andEarias insulana (Boisd.) larvae to azadirachtin and salannin

The effect of azadirachtin and salannin, two triterpenoids isolated from seeds of neem (Azadirachta indica A. Juss), on the feeding response ofSpodoptera littoralis (Boisd.) andEarias insulana (Boisd.) larvae, was investigated. Styropor (foamed polystyrene) lamellae were painted on both sides with a mixture of 5% sucrose with different concentrations of either azadirachtin or salannin dissoled in methanol-water (3∶7). Azadirachtin strongly suppressed feeding inS. littoralis larvae even at 0.001%, whereas salannin showed some antifeedant activity at 0.005% and above. Larvae ofE. insulana were deterred from feeding on azadirachtin-treated lamellae even at 0.005%, whereas salannin was effective only at 0.01% and above. Azadirachtin applied on cotton leaves deterred larvae ofS. littoralis from feeding at all concentrations ranging between 0.001 and 0.02%.     

芳香植物气味及提取液对茶尺蠖行为的影响

为了明确芳香植物对茶尺蠖Ectropisobliqua的驱避、拒食作用和获得应用于茶园茶尺蠖"推-拉"策略的植物材料,利用"Y"型嗅觉仪室内测定其成虫对芳香植物气味的趋性反应,并采用叶碟法测定芳香植物提取液对其幼虫的拒食作用及营养干扰效果。丁香罗勒、迷迭香、柠檬桉和芸香植株挥发物及甲醇提取液对茶尺蠖雌、雄成虫有显著的驱避效果。猫薄荷、迷迭香和鼠尾草的2 00 mg/mL甲醇提取液对茶尺蠖3龄幼虫表现出显著拒食活性,24 h后的选择性拒食率分别为93.85%、86.00%和77.32%,非选择性拒食率分别为85.77%、87.00%和88.05%。其中,迷迭香处理的幼虫生长率最低,仅为0.12 mg/天,对幼虫的相对取食量、食物利用率和食物转化率等营养指标有影响。研究表明,10种芳香植物中迷迭香具有显著的行为调控功能,是构建茶尺蠖"推-拉"策略的理想材料。     

雷公藤总生物碱对粘虫的生物活性

为进一步评价雷公藤中主要杀虫活性成分生物碱的杀虫活性及其应用前景,采用室内生测法研究了雷公藤总生物碱对粘虫Mythimnaseparate(Walker)取食、存活及生长发育等的影响。结果表明,雷公藤总生物碱对粘虫幼虫具较强的拒食活性,3、4、5龄幼虫24、48h的拒食中浓度(AFC50)分别为37.92、50.23、119.53mg·L-1和42.39、60.47、122.91mg·L-1;具有一定的胃毒活性,对粘虫3龄幼虫4、5天的LC50值分别为157.18mg·L-1和129.92mg·L-1;对粘虫幼虫的生长发育有明显抑制作用,表现在体重、体重增加量和相对生长率均显著降低,60mg·L-1处理组幼虫第2天体重、体重增加量、相对生长率比对照分别下降26.13%、42.74%和22.26%,幼虫龄期延长,存活率、化蛹率和成虫羽化率均明显下降,成虫产卵量减少;此外,还具有一定的杀卵作用,卵孵化率和初孵幼虫存活率明显降低。     

氯虫苯甲酰胺和氟虫双酰胺对不同虫态甜菜夜蛾的毒力作用

采用浸叶法、点滴法、夹毒叶片法、成虫药膜法、饲喂毒营养液法测定了氯虫苯甲酰胺、氟虫双酰胺对甜菜夜蛾卵、2~4龄幼虫、成虫的活性和对4龄幼虫的拒食活性,以明确氯虫苯甲酰胺和氟虫双酰胺对不同虫态甜菜夜蛾的毒力作用。结果表明,两种杀虫剂均不具有杀卵活性,但可以明显降低初孵幼虫存活率;氯虫苯甲酰胺、氟虫双酰胺均对2龄幼虫活性最高,分别为3龄幼虫的1.50、6.17倍和4龄幼虫的22.25、44.95倍,对4龄幼虫胃毒活性分别为触杀活性的14.10、8.44倍;氯虫苯甲酰胺对甜菜夜蛾成虫毒力为氟虫双酰胺的25.53~34.19倍。氯虫苯甲酰胺、氟虫双酰胺对甜菜夜蛾幼虫表现出较强的拒食作用, 至处理后48 h拒食率达到最高, 分别为 82.73%、84.15%,显著高于对照药剂甲维盐各浓度处理,处理试虫虫体皱缩、体节缩短,体重增加率明显低于对照和甲维盐各处理。     

Effects of mutations in Drosophila nicotinic acetylcholine receptor subunits on sensitivity to insecticides targeting nicotinic acetylcholine receptors

Several strains of Drosophila melanogaster possess mutant alleles in nicotinic acetylcholine receptor (nAChR) subunits, Dα1 and Dβ2 that confer resistance to neonicotinoids such as imidacloprid and nitenpyram, and Dα6, that confers resistance to spinosyns. These mutant strains were bioassayed with a selected set of nAChR active insecticides including neonicotinoids, spinosad, and sulfoxaflor, a new sulfoximine insecticide. All of the neonicotinoids examined, except dinotefuran showed reduced insecticidal efficacy on larvae of the Dα1 mutant, suggesting that this subunit may be important in the action of these insecticides. All of the neonicotinoids, including dinotefuran, showed reduced insecticidal efficacy on larvae possessing the Dβ2 mutation. A similar pattern of broad neonicotinoid resistance to that of Dβ2 alone was also observed for larvae with both the mutations (Dα1 + Dβ2). The Dβ2 mutation exhibited a lower level of cross-resistance to sulfoxaflor (<3-fold) than to any of the neonicotinoids (>13-fold). In contrast, there was no cross-resistance for any of the neonicotinoids or sulfoxaflor in adult flies with the Dα6 mutation, which confers high levels of resistance to spinosad. Thus in the D. melanogaster strains studied, target site resistance observed for the neonicotinoids and the spinosyns does not translate directly to resistance towards sulfoxaflor.     

Design, semisynthesis and insecticidal activity of novel podophyllotoxin derivatives against Brontispa longissima in vivo

In an attempt to find the effective phytopesticides, a series of novel podophyllotoxin derivatives were firstly synthesized and preliminarily tested for their antifeedant and insecticidal effects against the fifth-instar larvae of Brontispa longissima. The different antifeedant and insecticidal activity ranges of compounds 3a-l showed that variations of NR₁R₂ groups in the 4-position of podophyllotoxin skeleton markedly affected the activity profiles of this compound class, and some important SAR information has been revealed from it. To clarify their mode of action of insecticidal activity, the docking models as well as tubulin inhibitory effect of representative compound 3i were also investigated, and the result indicated that the insecticidal activity of these compounds was due to the tubulin inhibitory effect of these derivatives, thereby possibly providing some useful information for rational designs of novel podophyllotoxin-based insecticides.     

Biological activity of the essential oil from the leaves of Piper sarmentosum Roxb. (Piperaceae) and its chemical constituents on Brontispa longissima (Gestro) (Coleoptera: Hispidae)

The results showed that the essential oil from Piper sarmentosum has strong antifeedant and toxicity effects on Brontispa longissima. The best antifeedant and contact toxicity effects were observed in the 1st-2nd instar larvae. The essential oil also displayed a notable fumigation effect on the eggs and pupae of B. longissima. It took the control-treated insects 43.34 d to complete one generation, while the insects treated with 2000 mg/L essential oil needed 73.58 d. The essential oil was analyzed by gas chromatography/mass spectrometry and 41 components were identified. Myristicin (65.22%) and trans-caryophyllene (13.89%) were the major components. Myristicin exhibited strong antifeedant and contact toxicity effects on both the 3rd instar larvae and the imagoes of B. longissima, when it showed a significant fumigation effect on the eggs and pupae of B. longissima. Another P. sarmentosum essential oil and myristicin all showed a strong inhibiting effect on the growth and development of B. longissima along with the activity of AChE, CarE, GSTs and Na⁺, K⁺-ATPase in B. longissima larvae.     

溴氰虫酰胺和氯虫苯甲酰胺对三种鳞翅目害虫的毒力作用比较

为比较溴氰虫酰胺和氯虫苯甲酰胺对甜菜夜蛾、玉米螟和小地老虎的作用差异,采用浸卵法、浸叶法、饲喂毒营养液法等测定了溴氰虫酰胺和氯虫苯甲酰胺对3种害虫的卵、3龄幼虫和成虫的毒力,以及对其3龄幼虫的拒食活性。结果表明,溴氰虫酰胺和氯虫苯甲酰胺均无杀卵作用,但能降低初孵幼虫存活率。溴氰虫酰胺对甜菜夜蛾、玉米螟和小地老虎3龄幼虫的LC₅₀值分别为0.11、0.05和0.13 mg/L,相对毒力分别是氯虫苯甲酰胺的2.8、2.7和5.1倍。溴氰虫酰胺对3种害虫成虫的LC₅₀值分别为0.11、0.09和0.22 mg/L,相对毒力分别是氯虫苯甲酰胺的3.9、3.8和2.7倍。溴氰虫酰胺在亚致死浓度0.10、0.05和0.14 mg/L的剂量下分别对甜菜夜蛾、玉米螟和小地老虎3龄幼虫表现出较强的拒食作用,处理48 h后达到最高,拒食率分别为85.58%、81.91%和86.11%。药剂处理试虫虫体皱缩,体节缩短,体重增加率明显低于对照处理。表明溴氰虫酰胺对3种鳞翅目害虫的毒力作用比氯虫苯甲酰胺好,可作为氯虫苯甲酰胺的替代药品。     

The residual effect of a neem seed kernel extract sprayed on fodder beet against larvae ofSpodoptera littoralis

The residual effect of a dried methanolic extract of neem (Azadirachta indica A. Juss) seed kernels was investigated with larvae of the Egyptian cotton leafworm,Spodoptera littoralis (Boisd.), in field trials. Fodder beet was sprayed with 1% emulsions of the extract. The treated leaves were collected from the field 1, 3, 5 and 9 days after spraying and offered to the larvae for 48 h. Survival and mean weight of the larvae were recorded 2, 4, 6, 9 and 11 days from the start of exposure to the residues, and rate of pupation was calculated. The extract had a strong antifeedant effect and an intense insect growth-regulating (IGR) effect in field-treated leaves, especially with the 1- and 3-day-old residues. A positive correlation was found between the age of the residues and the mean percent of live larvae, larval weight and pupation rate of the larvae.     

Natural diterpene β-lactone derivative as photosystem II inhibitor on spinach chloroplasts

α,7β-Dihydroxyvouacapan-17β-oic acid (1) was isolated from Pterodon polygalaeflorus Benth. Then, (1) was modified to obtain 6α-hydroxyvouacapan-7β,17β-lactone (2). Inhibition properties of both (1) and (2) were evaluated in spinach chloroplasts. Only compound (2) inhibited non-cyclic electron transport and ATP synthesis, i.e., (2) behaved as a Hill reaction inhibitor. Compound (2) did not affect photosystem I (PSI) activity but it did inhibit electron flow through PSII. Analysis of the partial PSII reactions from water to DCPIP_ox, water to silicomolybdate, and diphenylcarbazide to DCPIP_ox allowed locating inhibition sites at (i) the oxygen-evolving complex (OEC) and (ii) the redox enzymes of the electron transport chain, in the span of P₆₈₀ to Q_A. Chlorophyll a fluorescence measurements confirmed the action site for (2).     

4β-卤代-4-脱氧鬼臼毒素和4β-氨基-4-脱氧鬼臼 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,设计合成了3个4β-卤代- 4-脱氧鬼臼毒素和4个4β-氨基- 4-脱氧鬼臼毒素类化合物,通过IR、MS、1H NMR和元素分析对其结构进行了确证。采用小叶碟添加法测试了合成化合物对3龄粘虫Mythimna separate幼虫24 h和48 h的拒食活性,结果表明: 4β-卤代- 4-脱氧鬼臼毒素类化合物的活性相对高于氨基取代产物、母体化合物鬼 臼毒素和对照品脱氧鬼臼毒素, 其中4β-溴代- 4-脱氧鬼臼毒素活性最高,其对粘虫幼虫24 h和48 h 的 AFC50分别为280.8和392.9 mg/L,分别是母体化合物鬼臼毒素的3.43和 1.90 倍,是对照品脱氧鬼臼毒素的2.46和1.57倍; 4β位引入氨基活性降低, 4β-叠氮衍生物的活性最低。     

Pesticidal properties of parthenin (from Parthenium hysterophorus) and related compounds

Eleven sesquiterpene lactone derivatives of parthenin ( 1 ), obtained from wild feverfew, Parthenium hysterophorus, were prepared by chemical and photochemical transformations. The compounds tested were a pyrazoline adduct ( 2 ) of parthenin, its cyclopropyl ( 3 ) and propenyl ( 4 ) derivatives, anhydroparthenin ( 5 ), a dihydro‐deoxygenated product ( 6 ), a formate ( 7 ) and its corresponding alcohol ( 8 ) and acetate ( 9 ), a rearranged product ( 10 ), lactone ( 11 ) and hemiacetal ( 12 ). All these derivatives, along with parthenin, were tried for their antifeedant action against sixth‐instar larvae of Spodoptera litura, for insecticidal activity against the adults of store grain pest Callosobruchus maculatus, for phytotoxic activity against Cassia tora, and for nematicidal activity against the juvenile stage‐II (J₂) of the root knot nematode Meloidogyne incognita. Antifeedent bioassay revealed that parthenin is moderately antifeedant. Among the derivatives, the saturated lactone ( 11 ) was found to be about 2.25 times more active than parthenin. The pyrazoline adduct ( 2 ) was found to be the most effective as an insecticide, with LC₅₀ values after 24, 48 and 72 h of 96, 43 and 32 mg litre⁻¹, respectively, which are comparable with neem extract. Compound 4 was found to be the most effective inhibitor of germination and seedling growth of C tora, with ID₅₀ values for germination, plumule length and radicle length of 136, 326 and 172 compared with 364, 738 and 427 mg litre⁻¹, respectively, for parthenin. Compound 10 was found to be the most effective in terms of nematicidal activity. The LC₅₀ values for this compound were 273 and 104 mg litre⁻¹, respectively, after 48 and 72 h compared with 862 and 512 mg litre⁻¹ observed for parthenin after 48 and 72 h. © 2001 Society of Chemical Industry     

Synthesis of novel derivatives of camptothecin as potential insecticides

In an attempt to find the biorational pesticides, a series of novel camptothecin derivatives were synthesized via a simple modification of the carbodiimide method using the combination of scandium triflate (Sc(OTf)₃) and 4-dimethylaminopyridine (DMAP), and their structures were identified by IR, ESR, HRMS and ¹H NMR. Their antifeedant effect and insecticidal activity against third-instar larva of Mythimna separate were examined. The results of preliminary bioassays showed that these compounds exhibited less potent antifeedant activity than camptothecin. Also, all of these derivatives of camptothecin showed delayed insecticidal activity, which differs from traditional neurotoxic insecticides. The results suggested that 20-hydroxyl group in the camptothecin derivatives is essential to keep the insecticidal activity and nature of the substitutes has a major impact on insecticidal activity of these compounds.     

The effect of IKI-7899, a new chitin synthesis inhibitor,on larvae ofTribolium castaneum andSpodoptera littoralis

The effect of IKI-7899 and diflubenzuron on larval development and emergence ofTribolium castaneum and ofSpodoptera littoralis was determined. The LC₅₀ of IKI-7899 at adult emergence ofT. castaneum larvae fed the compound in their diet and the ED₅₀ of S.littoralis larvae treated topically were approximately one-sixth those of diflubenzuron.     

鬼臼毒素4β含硫衍生物的 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,在前期研究基础上设计合成了3个4β-硫酯-4-脱氧鬼臼毒素、2个4β-硫醚-4-脱氧鬼臼毒素及4β-巯基-4-脱氧鬼臼毒素共6个未见文献报道的化合物。其结构经IR、MS、1H NMR和元素分析确证。采用小叶碟添加法测试了化合物对3龄粘虫Mythimna separate幼虫的拒食活性,结果表明:4β-巯基-4-脱氧鬼臼毒素的活性最高,24和48 h 的AFC50(拒食中浓度)分别为164.6 和248.1 mg/L,分别是母体化合物鬼臼毒素活性的5.8和 3.0倍。引入硫醚及硫酯后活性均降低。     

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。