Antifeedant/insecticidal terpenes from asteraceae and labiatae species native to Argentinean semi-arid lands

To validate the potential as added-value resources of Asteraceae and Labiatae species of Argentinean semi-arid lands, we have selected 13 of their major terpenoids belonging to several chemical classes and tested their insect antifeedant and toxic activity on the herbivorous insects Spodoptera littoralis and Leptinotarsa decemlineata. The antifeedant effects of the test compounds were structure- and species-dependent. The most active antifeedant to L. decemlineata was the eudesmane sesquiterpene gamma-costic acid (13), followed by the labdane diterpene 2alpha,3alpha-dihydroxycativic acid (8), the clerodane diterpenes 6-acetylteucjaponin B (5), bacchotricuneatin A (1), bartemidiolide (7), butanolide (4), and the sesquiterpenes ilicic acid (11) and tessaric acid (10) (eudesmane and eremophilane type, respectively). S. littoralis was only affected by the clerodanes and showed the strongest response to salviarin (3) and 5, followed by hawtriwaic acid (6) and 12-epi-bacchotricuneatin A (2). Orally injected S. littoralis larvae were negatively affected by 5. Most of the diterpenes had selective cytotoxic effects to insect-derived Sf9 cells with the clerodane 1 being the most active, followed by the eudesmane costic acid (12), the only cytotoxic sesquiterpene. None of these compounds was cytotoxic to mammalian CHO cells.     

Antifeedant and phytotoxic activity of hydroxyperezone and related molecules

The insect antifeedant and toxic activity of hydroxyperezone (1), its derivatives 2-9, along with 3-hydroxy- (10) and 6-hydroxythymoquinone (11) were studied against Spodoptera littoralis, Leptinotarsa decemlineata, and Myzus persicae. The antifeedant tests showed that L. decemlineata was the most sensitive insect, followed by M. persicae, while S. littoralis was not deterred by compounds 1-11. Leucohydroxyperezone tetraacetate (3), oxoperezinone (6), dihydroleucoperezinone diacetate (7), 3-hydroxy- (10) and 6-hydroxythymoquinone (11) showed strong activity against L. decemlineata. 1 and 7 exhibited moderate deterrent activity against M. persicae, while 1 and dihydroleucohydroxyperezone tetraacetate (4) acted as post-ingestive antifeedants to S. littoralis. The phytotoxic activity of compounds 1-11 was also evaluated. Hydroxyperezone (1) strongly inhibited seed germination at 24 h, while the activity of 3-8 and 10 was moderate. The level of radicle growth inhibition obtained with compounds 1-5 and 8-11 was significant (< 50%).     

Semisynthetic derivatives of ent-kauranes and their antifeedant activity

Chemical modification of functional groups on linearol yielded several ent-kaurane derivatives. These compounds were tested for their antifeedant activity against larvae of Spodoptera littoralis. Although linearol did not influence the feeding behaviour of larvae, some of its derivatives showed significant antifeedant activity.     

Antifeeding Active Substances for Insect in Caryopteris divaricata Maxim.

Six antifeeding active diterpenes having a clerodane skeleton, clerodin (I), caryoptin (II), dihydroc?erodin-I (V), dihydrocaryoptin (VI), clerodin hemiacetal (VII), and caryoptin hemi- acetal (VIII), were isolated from Caryopteris divaricata Maxim. Antifeeding activities of six compounds and these derivatives against the 3rd instar larvae of Spodoptera litura F. were tested by the leaf disk method. In addition, the terms of “relative antifeedant” and “absolute antifeedant” were proposed for the antifeeding substances, and the latter term was used to the above six diterpenes.     

Antifeedant activity of some polygodial derivatives

Polygodial (1) and its derivatives acetal 2 (propylene) and 3 (ethylene) were prepared and their antifeedant activity and toxic effects evaluated on several insect species with different feeding ecologies (Spodoptera littoralis, Leptinotarsa decemlineata, Myzus persicae and Rhopalosiphum padi) along with that of polygonone (4). We also tested their selective cytotoxic effects on insect-derived (Spodoptera frugiperda ovarian Sf9 cells) and mammalian Chinese hamster ovary (CHO) cells. The antifeedant activity of these compounds was consistent with the proposed mode of action for antifeedant drimanes, i. e. adduct formation with amino groups for M. persicae and R. padi (dialdehyde > ketoaldehyde > aldehydeacetal). This was not the case for L. decemlineata, and the cytotoxic effects on insect-derived Sf9 and mammalian CHO cells (aldehydeacetal > dialdehyde > ketoaldehyde).     

Antifeedant and phytotoxic activity of cacalolides and eremophilanolides

The antifeedant effect of six cacalolides and six eremophilanolides was tested against the herbivorous insects Spodoptera littoralis, Leptinotarsa decemlineata, and Myzus persicae. The test compounds included several natural products isolated from Senecio madagascariensis (14-isovaleryloxy-1,2-dehydrocacalol methyl ether, 4), S. barba-johannis (13-hydroxy-14-oxocacalohastine, 5; 13-acetyloxy-14-oxocacalohastine, 6) and S. toluccanus [6-hydroxyeuryopsin, 7; 1(10)-epoxy-6-hydroxyeuryopsin, 9; toluccanolide A, 11] and the derivatives cacalol methyl ether (1); cacalol acetate (2); 1-acetyloxy-2-methyloxy-1,2,3,4-tetradehydrocacalol acetate (3); 6-acetyloxyeuryopsin (8); 6-acetyloxy-1(10)-epoxyeuryopsin (10), and toluccanolide A acetate (12). Compound 11 and its derivative 12 exhibited moderate antifeedant activity against S. littoralis; 2, 7-10, and 12 showed strong activity against L. decemlineata, while the aphid M. persicae was moderately deterred in the presence of compounds 1, 4, 8, 10, and 12. The phytotoxic activity of 1-12 on Lactuca sativa was also evaluated. Compounds 2 and 4-12 moderately inhibited seed germination at 24 h, while compounds 1-4, 6, 9, and 10 had a significant inhibition effect on L. sativa radicle length (over 50%).     

Synergism of diacylhydrazine insecticides with metyrapone and diethylmaleate

Abstract:  The two metabolic synergists, metyrapone (2-methyl 1,2-di-3-pyridyl-1-propanone) and diethylmaleate could increase the toxicity of the three most recent diacylhydrazines, representing a novel group of insect growth regulators (IGRs). These components are known as respective inhibitors of oxidative and glutathione S-transferase enzymes. Larvicidal toxicity was tested in the laboratory by oral treatment against last-instar larvae of the Colorado potato beetle Leptinotarsa decemlineata (Say) and of the beet armyworm Spodoptera exigua (Hübner). The obtained results should enable to improve the activity of tebufenozide, methoxyfenozide and halofenozide, and it may be used to suggest potential mechanisms for resistance against this novel group of IGRs, that is important to counteract cross-resistance with other insecticide groups.     

Antifeedant activity of fatty acid esters and phytosterols from Echium wildpretii

Crude extracts and fractions from Echium wildpretii H. Pearson ex Hook. f. subsp. wildpretii (Boraginaceae) have been tested against insect species Spodoptera littoralis, Leptinotarsa decemlineata, and the aphids Myzus persicae, Diuraphis noxia, Metopolophium dirhodum, Rhopalosiphum maidis, and Rhopalosiphum padi. The EtOH extract and the lipid and steroidal fractions of E. wildpretii exhibited significant antifeedant activities against the aphids and L. decemlineata. Two bioactive mixtures composed of fatty acid esters and n-alkanes were obtained from the lipid fraction. The bioguided fractionation of the steroidal fraction resulted in the isolation of glutinol, β-sitosterol, (3β,7α)-stigmast-5-ene-3,7-diol, and (3β,7α)-7-methoxystigmast-5-en-3-ol. The latter two compounds exhibited potent antifeedant activities against L. decemlineata indicating that the presence of an O-bearing C(7) was responsible for the activities of these molecules.     

斑点野生稻拒食活性组分的分离及其对斜纹夜蛾消化酶活性的影响

为了进一步评估斑点野生稻Oryza punctata的抗虫性,采用液 液分配萃取和硅胶柱层析的方法,从斑点野生稻甲醇提取物中分离获得石油醚、氯仿、乙酸乙酯、正丁醇和水的萃取物,测定了其对斜纹夜蛾Spodoptera litura 3龄幼虫拒食活性。结果显示,氯仿萃取物比其他4种萃取物具有更高的拒食活性,在25 mg/mL的浓度下,24 h和48 h的拒食率分别为55.62%和52.66%。氯仿萃取物经硅胶柱层析后,得到14个组分。比较14个组分的拒食活性,发现组分4和10为主要的活性组分。这两个组分对斜纹夜蛾幼虫中肠脂肪酶和α-淀粉酶的活性都具有一定的抑制活性,其中组分10对脂肪酶具有显著的抑制效果,以1 mg/mL的浓度活体处理48 h和72 h抑制率分别达19.82％和34.60％; 对α-淀粉酶的影响在48 h和72 h内都具有显著的抑制效果,随着处理时间的延长,其抑制率逐步提高,72 h的抑制率分别为25.06％和27.40％。结果提示斜纹夜蛾幼虫中肠脂肪酶和α-淀粉酶可能是斑点野生稻拒食活性成分的作用靶标。     

Antifeedant C20 diterpene alkaloids

We have tested the insect antifeedant and toxic activity of 21 C20 diterpenoid alkaloids on Spodoptera littoralis and Leptinotarsa decemlineata. The antifeedant effects of the test compounds were structure- and species-dependent. The most active antifeedants to L. decemlineata and S. littoralis were the rearranged form of hetisine (20; EC50 = 1.7 microg/cm2) and 19-oxodihydroatisine (9; EC50 = 0.1 microg/cm2), resp. Glandulosine (8) moderately affected orally injected S. littoralis larvae. A few compounds (13-oxocardiopetamine (4), 9, and atisinium chloride (13)) had cytotoxic effects to insect-derived Sf9 cells with varying degrees of selectivity with respect to mammalian CHO cells. Compounds 4 and 15,22-O-diacetyl-19-oxodihydroatisine (10) increased Trypanosoma cruzi mortality. Our results support the plant protective role of C20 diterpenoid alkaloids and open a new field for parasite control strategies.     

竹提取物对棉铃虫幼虫及菜青虫的拒食活性

研究结果表明 ,质量浓度为 1 0g L的 1 0种供试竹提取物对棉Helicoverpaarmigera铃虫均具有较强的拒食作用 ,1 2h拒食率最高达 95 . 0 3 % ,最低为 74. 0 7% ,其中毛金竹 (Phyllostachysnigravar.henonis)、白纹短穗竹 (Brachystachyumalbostriatum)提取物对棉铃虫 3龄幼虫的AFC50 (拒食中浓度 )分别为 2 . 0g L、2. 7g L ,但 2 4h、48h拒食率均明显下降。对菜青虫 3龄pierisrapae幼虫的拒食效果以凤凰竹 (Bambusamultiplex)提取物最好 ,2 4h拒食率为 71. 69% ;对 4龄菜青虫的拒食效果以毛金竹提取物最好 ,拒食率为71 . 45 % ,其中毛金竹、白纹短穗竹 2种竹提取物对菜青虫 3龄幼虫的AFC50 分别为 2 .68g L和 3 . 3 7g L。研究结果对于开发环境友好农药以及充分利用竹类资源均具有重要意义。     

海木提取物对菜青虫幼虫的生物活性

测试了海木提取物对菜青虫幼虫的拒食活性,并对拒食活性高的部分进行了乙酰胆碱酯酶活性、蛋白水解酶活性等测定。海木的氯仿部分表现出明显的拒食活性(拒食率97.7%),同时还能抑制菜青虫的乙酰胆碱酯酶活性,提高蛋白水解酶活性,降低菜青虫体内蛋白质含量。     

Chlorantraniliprole susceptibility in Leptinotarsa decemlineata in the north Xinjiang Uygur autonomous region in China

The Colorado potato beetle (Leptinotarsa decemlineata (Say)) in the north Xinjiang Uygur autonomous region has evolved resistance to various types of insecticides. Chlorantraniliprole is a novel anthranilic diamide insecticide that binds and activates ryanodine receptors. It exhibited excellent efficacy against L. decemlineata in several field trails in Europe. In the present paper, the susceptibility of L. decemlineata fourth-instar larvae derived from six field populations and L. decemlineata adults derived from three field populations to chlorantraniliprole was determined by a topical application. The fourth-instar larvae were substantially more susceptible to chlorantraniliprole than adults, although the range of susceptibility was far greater among the fourth-instar larvae. Regarding stomach toxicities, adult beetles were less susceptible to chlorantraniliprole than larvae. Chlorantraniliprole was most toxic to second-instar larvae, followed by third- and fourth-instar larvae. These data suggested that the appropriate timing for chlorantraniliprole spraying is the early larval stage. Moreover, the synergistic activities of chlorantraniliprole in combination with triphenyl phosphate, diethyl maleate, or piperonyl butoxide against fourth-instar larvae from two field populations and adults from one field population were tested. Piperonyl butoxide had synergistic effects with chlorantraniliprole against fourth-instar larvae but not against adult beetles. Conversely, triphenyl phosphate and diethyl maleate exerted little synergistic effects. It appears that there is a potential risk of resistance against chlorantraniliprole resulting from cytochrome P450 monooxygenase activity.     

Bioefficacy and mode-of-action of some limonoids of salannin group fromAzadirachta indica A. Juss and their role in a multicomponent system against lepidopteran larvae

Biological activities of the salannin type of limonoids isolated fromAzadirachta indica A. Juss were assessed using the gram pod borerHelicoverpa armigera (Hubner) and the tobacco armywormSpodoptera litura (Fabricius) (Lepidoptera: Noctuidae). Inhibition of larval growth was concomitant with reduced feeding by neonate and third instar larvae. All three compounds exhibited strong antifeedant activity in a choice leaf disc bioassay with 2.0, 2.3 and 2.8 (μ/cm² of 3-O-acetyl salannol, salannol and salannin, respectively deterring feeding by 50% inS. litura larvae. In nutritional assays, all three comounds reduced growth and consumption when fed to larvae without any effect on efficiency of conversion of ingested food (ECI), suggesting antifeedant activity alone. No toxicity was observed nor was there any significant affect on nutritional indices following topical application, further suggesting specific action as feeding deterrents. When relative growth rates were plotted against relative consumption rates, growth efficiency of theH. armigera fed diet containing 3-O-acetyl salannol, salannol or salannin did not differ from that of starved control larvae (used as calibration curve), further confirming the specific antifeedant action of salannin type of limonoids. Where the three compounds were co-administered, no enhancement in activity was observed. Non-azadirachtin limonoids having structural similarities and explicitly similar modes of action, like feeding deterrence in the present case, have no potentiating effect in any combination.     

Selective action of acetogenin mitochondrial complex I inhibitors

Five annonaceous acetogenins, rolliniastatin-1 [structure: see text], rolliniastatin-2 [structure: see text], laherradurin [structure: see text], squamocin [structure: see text], annonacin [structure: see text], and rotenone as a reference, differing in their NADH oxidase inhibition activity, have been evaluated for antifeedant, insecticidal, trypanocidal and cytotoxic effects on insect, mammalian and tumor cells. All the test compounds were toxic to Leptinotarsa decemlineata, demonstrated selective cytotoxicity to insect Sf9 cells and a panel of tumor cell lines with the multidrug-resistant SW480 (P-glycoprotein+, Pgp+) being the most sensitive one. Compounds [structure: see text] and rotenone had post-ingestive effects against Spodoptera littoralis larvae while [structure: see text] and rotenone were active against Trypanosoma cruzi. Based on their biochemical properties (inhibition of the mitochondrial NADH oxidase activity), the in vivo effects of these compounds on S. littoralis and their cytotoxic effects on Sf9 and tumor cells were more predictable than their effect on T. cruzi and mammalian cells.     

Polyoxygenated cyclohexane derivatives and other constituents from Kaempferia rotunda L

Methanol extracts of Kaempferia rotunda L. rhizomes yielded seven compounds including six polyoxygenated cyclohexane derivatives identified as (-)-6-acetylzeylenol (1), four acylated derivatives of 1-benzoyloxymethyl-1,6-epoxycyclohexan-2,3,4,5-tetrol (3-6), a Diels-Alder adduct of 3-benzoyl-1-benzoyloxymethylcyclohexa-4,6-dien-2,3-diol (7), and a triacylated derivative of salicin (9). The cyclohexane diepoxide, crotepoxide (8), was also obtained. Spectroscopic methods were used for structure determination. The methanol extract of the rhizomes of K. rotunda and (-)-2-acetyl-4-benzoyl-1-benzoyloxymethyl-1,6-epoxycyclohexan-2,3,4,5-tetrol (2-acetylrotepoxide B; 6), had antifeedant activity against larvae of Spodoptera littoralis. (-)-Zeylenol (2) also showed antifeedant activity, whereas (-)-6-acetylzeylenol (1) was inactive.     

Minor diterpenes from Persea indica: their antifeedant activity

The new diterpenes anhydrocinnzeylanone, garajonone and 2,3-didehydrocinnzeylanone, and the known anhydrocinnzeylanine, have been isolated from Persea indica. The antifeedant activity of these compounds has been evaluated showing the importance of the 11-hemiketal group for the antifeedant effects of ryanodane diterpenes.     

Effects and modes of action of citrus limonoids against Leptinotarsa decemlineata

ABSTRACT Limonin and its five derivatives were evaluated in feeding bioassays for depression effects on feeding, growth and development of the fourth stadium Leptinotarsa decemlineata (Say) (Coleoptera: Chrysomelidae). Epilimonol and limonin diosphenol were most effective in depression of feeding and growth, with ED₅₀s 10 and 8 μg/cm². At a dosage of 31.6 μg/cm², epilimonol, limonin diosphenol and limonin caused both significant feeding reduction and developmental delay, while deoxylimonol, tetrahydrolimonin and limonol were not effective. Mouth-part coating and antifeedant bioassays show that feeding inhibition at host acceptance level seems to be the primary mode of action of epilimonol and limonin diosphenol.     

红楝提取物对菜青虫幼虫的生物活性

对红楝的乙酸乙酯抽提部分进行了粗分并对各部分进行了拒食活性测试,并对活性较高的部分进行了乙酰胆碱酯酶活性、蛋白酶活性、蛋白质含量等测定。编号为6的部分拒食率最高为60．9％。在对其进行进一步研究中发现红楝对幕青虫的神经系统影响较明显,而胃毒毒性却不十分理想。     

Antifeedant and Insecticidal Activity of Quassinoids against Diamondback Moth (Plutella xylostella)

The antifeedant and insecticidal activities of sixteen quassinoids against 3rd instar larvae of the diamondback moth (Plutella xylostella) were compared with those of known insect antifeedant chlordimeform (1), and the structure-activity relationship was discussed. The insecticidal activity of quassin (2) was higher than that of 1, although its antifeedant activity was nearly the same as that of the reference compound.