Allelochemical Potential of Callicarpa acuminata

The allelochemical potential of Callicarpa acuminata (Verbenaceae) was investigated by using a biodirected fractionation study as part of a long-term project to search for bioactive compounds among the rich biodiversity of plant communities in the Ecological Reserve El Eden, Quintana Roo, Mexico. Aqueous leachate, chloroform-methanol extract, and chromatographic fractions of the leaves of C. acuminata inhibited the root growth of test plants (23-70%). Some of these treatments caused a moderate inhibition of the radial growth of two phytopathogenic fungi, Helminthosporium longirostratum and Alternaria solani (18-31%). The chloroform-methanol (1:1) extract prepared from the leaves rendered five compounds: isopimaric acid (1), a mixture of two diterpenols [sandaracopimaradien-19-ol (3) and akhdarenol (4)], alpha-amyrin (5), and the flavone salvigenin (6)]. The phytotoxicity exhibited by several fractions and the full extract almost disappeared when pure compounds were evaluated on the test plants, suggesting a synergistic or additive effect. Compounds (4), (5), and the semisynthetic derivative isopimaric acid methyl ether (2) had antifeedant effects on Leptinotarsa decemlineata. Compound 5 was most toxic to this insect, followed by (2), (4), and (6) with moderate to low toxicity. No correlation was found between antifeedant and toxic effects on this insect, suggesting that different modes of action were involved. All the test compounds were cytotoxic to insect Sf9 cells while (6), (4), and (1) also affected mammalian Chinese Hamster Ovary (CHO) cells. Compound 5 showed the strongest selectivity against insect cells. This study contributes to the knowledge of the defensive chemistry and added value of C. acuminata.     

Antifeedant and Phytotoxic Activity of the Sesquiterpene <Emphasis Type="Italic">p</Emphasis>-Benzoquinone Perezone and Some of its Derivatives

The sesquiterpene p-benzoquinone perezone (1), isolated from Perezia adnata var. alamani (Asteraceae), and its non-natural derivatives isoperezone (2), dihydroperezone (3), dihydroisoperezone (4), and anilidoperezone (5) were tested as antifeedants against the herbivorous insects Spodoptera littoralis, Leptinotarsa decemlineata, and Myzus persicae. Compounds 1-5 exhibited strong antifeedant activity against L. decemlineata and M. persicae, and elicited a low response by S. littoralis. Antifeedant activity on L. decemlineata and M. persicae increased when the hydroxyl group at C-3 in perezone (1) was changed to C-6 to give isoperezone (2). The same effect was found with hydrogenation of the double bond of the alkyl chain of (1) to yield dihydroperezone (3). In contrast, hydrogenation of this double bond in isoperezone (2) to give dihydroisoperezone (4) led to a reduction in antifeedant activity. Determination of the phytotoxic activity of 1-5 revealed that 3 had a significant inhibition effect on Lactuca sativa radicle length growth.     

Insecticidal Triterpenes in Meliaceae: Plant Species,Molecules, and Activities: Part II (Cipadessa,Melia)

Plant-originated triterpenes are important insecticidal molecules. Research on the insecticidal activity of molecules from Meliaceae plants has always been a hotspot due to the molecules from this family showing a variety of insecticidal activities with diverse mechanisms of action. In this paper, we discussed 116 triterpenoid molecules with insecticidal activity from 22 plant species of five genera (Cipadessa, Entandrophragma, Guarea, Khaya, and Melia) in Meliaceae. In these genera, the insecticidal activities of plants from Entandrophragma and Melia have attracted substantial research attention in recent years. Specifically, the insecticidal activities of plants from Melia have been systemically studied for several decades. In total, the 116 insecticidal chemicals consisted of 34 ring-intact limonoids, 31 ring-seco limonoids, 48 rearranged limonoids, and 3 tetracyclic triterpenes. Furthermore, the 34 ring-intact limonoids included 29 trichilin-class chemicals, 3 azadirone-class chemicals, and 1 cedrelone-class and 1 havanensin-class limonoid. The 31 ring-seco limonoids consisted of 16 C-seco group chemicals, 8 B,D-seco group chemicals, 4 A,B-seco group chemicals, and 3 D-seco group chemicals. Furthermore, among the 48 rearranged limonoids, 46 were 2,30-linkage group chemicals and 2 were 10,11-linkage group chemicals. Specifically, the 46 chemicals belonging to the 2,30-linkage group could be subdivided into 24 mexicanolide-class chemicals and 22 phragmalin-class chemicals. Additionally, the three tetracyclic triterpenes were three protolimonoids. To sum up, 80 chemicals isolated from 19 plant species exhibited antifeedant activity toward 14 insect species; 18 chemicals isolated from 17 plant species exhibited poisonous activity toward 10 insect species; 16 chemicals isolated from 11 plant species possessed growth-regulatory activity toward 8 insect species. In particular, toosendanin was the most effective antifeedant and insect growth-regulatory agent. The antifeedant activity of toosendanin was significant. Owing to its high effect, toosendanin has been commercially applied. Three other molecules, 1,3-dicinnamoyl-11-hydroxymeliacarpin, 1-cinnamoyl-3-methacryl-11-hydroxymeliacarpin, and 1-cinnamoyl-3-acetyl-11-hydroxymeliacarpin, isolated from Melia azedarach, exhibited a highly poisonous effect on Spodoptera littoralis; thus, they deserve further attention.     

Insecticidal Triterpenes in Meliaceae: Plant Species,Molecules and Activities: Part Ⅰ (Aphanamixis-Chukrasia)

Plant-originated triterpenes are important insecticidal molecules. The research on insecticidal activity of molecules from Meliaceae plants has always received attention due to the molecules from this family showing a variety of insecticidal activities with diverse mechanisms of action. In this paper, we discuss 102 triterpenoid molecules with insecticidal activity of plants of eight genera (Aglaia, Aphanamixis, Azadirachta, Cabralea, Carapa, Cedrela, Chisocheton, and Chukrasia) in Meliaceae. In total, 19 insecticidal plant species are presented. Among these species, Azadirachta indica A. Juss is the most well-known insecticidal plant and azadirachtin is the active molecule most widely recognized and highly effective botanical insecticide. However, it is noteworthy that six species from Cedrela were reported to show insecticidal activity and deserve future study. In this paper, a total of 102 insecticidal molecules are summarized, including 96 nortriterpenes, 4 tetracyclic triterpenes, and 2 pentacyclic triterpenes. Results showed antifeedant activity, growth inhibition activity, poisonous activity, or other activities. Among them, 43 molecules from 15 plant species showed antifeedant activity against 16 insect species, 49 molecules from 14 plant species exhibited poisonous activity on 10 insect species, and 19 molecules from 11 plant species possessed growth regulatory activity on 12 insect species. Among these molecules, azadirachtins were found to be the most successful botanical insecticides. Still, other molecules possessed more than one type of obvious activity, including 7-deacetylgedunin, salannin, gedunin, azadirone, salannol, azadiradione, and methyl angolensate. Most of these molecules are only in the primary stage of study activity; their mechanism of action and structure–activity relationship warrant further study.     

Insect antifeedant activity associated with compounds isolated from species ofLonchocarpus andTephrosia

The antifeedant activity of a series of 21 chalcones, flavanes, and flavanones isolated from the generaLonchocarpus andTephrosia (Leguminosae) was assessed by behavioral and electrophysiological bioassays against larvae ofSpodoptera littoralis andS. exempta. The antifeedant activity is related to the molecular structure of the compounds, and possible modes of interaction with the insect taste receptors are discussed.     

麻疯树种子提取物对几种害虫的杀虫活性

在室内测定并比较了3种麻疯树种子提取物对同翅目、鳞翅目和鞘翅目害虫桃蚜、菜青虫和米象的杀虫活性。结果显示种子油、种子乙醇提取物和石油醚提取物对3种害虫都具有一定杀虫活性，对桃蚜的触杀活性LC50分别为5．1154、2．0796、13．9882g／L；对米象的杀虫活性LC50分别为8．0243、3．0701、24．3458g／L；种子油和乙醇提取物对菜青虫的胃毒活性LC加分别为18．1043、3．0796g／L，此外这2种提取物对菜青虫也显示出较强的拒食活性；而种子石油醚提取物对菜青虫无明显胃毒活性，拒食活性也很弱。麻疯树种子提取物对3种害虫的相对毒力顺序为乙醇提取物〉种子油〉石油醚提取物。     

A new method for fast isolation of insect antifeedant compounds from complex mixtures

Bioassay-guided isolation of bioactive natural substances requires monitoring of all fractionation and purification steps using a bioassay system. This is often a long and tedious process, especially with insect feeding bioassays. We report here a new method, based on the principle of bioautography, for a quick isolation of insect antifeedant compounds. TLC plates, after development, are coated with a thin layer of artificial diet and fed toSpodoptera litura larvae. The location of uneaten areas is then compared with theR _fvalues of the TLC spots, in order to determine rapidly the active fractions. This methods allows for a very fast determination of the most active antifeedant compounds in a complex mixture and considerably speeds up the isolation process. This new method was successfully applied in the study of antifeedant activity of several plant samples, and results are presented here for a model plant,Skimmia japonica (Rutaceae). Using this new method, the compounds responsible for the feeding-deterrent activity, three furanocoumarins (bergapten, xanthotoxin, and oxypeucedanin), were quickly and efficiently identified.     

Antifeedant Compounds from Three Species of Apiaceae Active Against the Field Slug, Deroceras reticulatum (Muller)

Extracts of volatiles from foliage of three plants in the Apiaceae, Conium maculatum L. (hemlock), Coriandrum sativum L. (coriander), and Petroselinum crispum Mill. (Nym.) (parsley), previously shown to exhibit antifeedant activity in assays with the field slug, Deroceras reticulatum (Muller) (Limacidae: Pulmonata), were studied further to identify the active components. Coupled gas chromatography-mass spectrometry (GC-MS) and neurophysiological assays using tentacle nerve preparations resulted in the identification of 11 active compounds from the three extracts. Wheat flour feeding bioassays were used to determine which of these compounds had the highest antifeedant activity. One of the most active compounds was the alkaloid gamma-coniceine, from C. maculatum. The role of potentially toxic alkaloids as semiochemicals and the potential for using such compounds as crop protection agents to prevent slug feeding damage is discussed.     

Patterns of Bioactivity and Herbivory on Nothofagus Species from Chile and New Zealand

Nothofagus species from Chile and New Zealand were surveyed in the field for invertebrate abundance and leaf feeding damage and in the laboratory for antifeedant activity against leafrollers (Ctenopsteustis obliquana, Epiphyas postvittana), deterrent activity against pea aphid (Acyrthosiphon pisum), insect growth regulatory activity (Oncopeltus fasciatus), nematicidal activity (Caenorhabditis elegans), antibiotic activity (Pseudomonas solanaciarium), and general toxicity. A data matrix indicated that N. alessandri and N. pumilio most likely have a chemical barrier to insect attack as leaves showed low faunal abundance, low herbivory, and activity in the leafroller antifeedant, aphid deterrent, and nematicidal assays. A chemical examination of N. alessandri that used the leafroller antifeedant test to guide the separation yielded an active fraction containing the flavonoid, galangin, and the stilbene, pinosylvin, which appear to act in concert to deter leafroller feeding. The discovery of the phytoalexin, pinosylvin, in the leaves, raises the possibility that Nothofagus in general, and N. alessandri in particular, may have induced chemical defense mechanisms.     

Extractives of seeds of the meliaceae: Effects onSpodoptera frugiperda (J.E. Smith),Acalymma vittatum (F.), andArtemia salina Leach

Hexane and ethanol extracts of seeds from 22 species of plants of the family Meliaceae from a number of countries were prepared. The extracts were submitted to antifeedant and toxicity bioassays utilizing fall armyworm [Spodoptera frugiperda (J.E. Smith)] (Lepidoptera: Noctuidae) larvae and striped cucumber beetle [Acalymma vittatum (F.)] (Coleoptera: Chrysomelidae) adults. Toxicity tests were also performed with brine shrimp,Anemia salina Leach. Feeding inhibition and mortality produced by some of these extracts were comparable to and, in certain cases, slightly greater than the effects produced by comparable neem (Azadiracta indica A. Juss.) seed preparations. Brine shrimp toxicity data do not extrapolate to insect activity, and vice versa.Presented at the national meeting of the Entomological Society of America in Hollywood, Florida, December 8–12, 1985.Mention of firm or product names does not imply recommendation or endorsement by USDA over others not mentioned.     

Photooxidation of Nimbin and Salannin, Tetranortriterpenoids from the Neem Tree (Azadirachta indica)

Nimbin and salannin, major triterpenoids accompanying azadirachtin in extracts of neem (Azadirachta indica) seeds, were photooxidized by UV light in the presence of oxygen to more polar, unstable intermediates that rearranged on silica gel to two final products in which the furan ring had been oxidized to isomeric hydroxybutenolides. The isomeric hydroxybutenolides were also readily formed when a crude extract of triterpenoids from neem seeds was irradiated, and both isomers of salannin have been isolated from seeds. Photooxidation of nimbin and salannin proceeded much faster than that of azadirachtin. All photoproducts showed some biological activity againstSpodoptera littoralis, Locusta migratoria, andSchistocerca gregaria. Isonimbinolide was as potent as azadirachtin at inhibiting feeding in all three species, and it also inhibited the growth ofS. littoralis. Isosalanninolide showed potent antifeedant and growth inhibitory activity againstS. littoralis.     

Effects ofneo-clerodane diterpenes fromTeucrium on feeding behavior of colorado potato beetle larvae

Treatment of potato leaf disks with fourneo-clerodane diterpenes fromTeucrium (eriocephalin, teucrin-A, teucvin, and teuscorolide) significantly reduced feeding by larvae ofLeptinotarsa decemlineata (Colorado potato beetle). Choice and no-choice tests suggest that teuscorolide acts as a feeding deterrent, whereas the antifeedant activity of teucrin-A, teucvin, and eriocephalin is likely associated with a toxic mode of action. Nutritional tests, antifeedant simulation assays, and posttreatment studies confirmed that teucrin-A can be categorized by its mode of action as a toxin, rather than as a feeding deterrent.     

Antifeedant and toxic effects of sesquiterpenes fromSenecio palmensis to colorado potato beetle

A bioassay-guided fractionation of the aerial parts ofSenecio palmensis resulted in the isolation of two sesquiterpenes, 2,10-bisaboladien-1-one and 11-acetoxy-5-angeloyloxy-silphinen-3-one. The bisabolene and the silphinene represented 0.012% and 0.024% of the plant dry weight, respectively. Both compounds showed antifeedant activity againstLeptinotarsa decemlineata larvae and adults in short-term choice and no-choice bioassays. Both compounds were also tested against different species of phytopathogenic fungi. The beetles were more sensitive to these compounds in choice than in no-choice assays, with a gradient of increasing sensitivity from second instars to adults. Bisabolene was 45 times less active as an antifeedant than juglone, which was tested as a positive control. The silphinen was more active than the bisabolene, with a range of activity similar to juglone. Furthermore, exposure of fourth instars to these compounds over a 24-hr period resulted in reduced feeding and growth rates. To distinguish between antifeedant and toxic effects, growth efficiencies were calculated as the slope of the regression of relative growth rate on relative consumption rate. The comparison of these results with those of antifeedant simulation and contact toxicity bioassays indicates that feeding inhibition is the primary mode of action of the bisabolene, while the silphinene shows both antifeedant and toxic effects.     

The influence of dietaryβ-carboline alkaloids on growth rate,food consumption,and food utilization of larvae ofSpodoptera exigua (Hubner)

-Carboline alkaloids are found worldwide in many plant families. Harman, harmine, and other simple -carboline alkaloids were tested for activity against a generalist phytophagous insect, the beet army worm [Spodoptera exigua (Hubner)]. Chronic dietary exposure tests (neonate to pupa) reveal potent antifeedant and possible toxic effects. Acute dietary exposure tests on fifth-instar larvae also demonstrate antifeedant activity.     

A new bioassay for testing plant extracts and pure compounds using red flour beetleTribolium castaneum Herbst

We designed a new bioassay to test plant extract activity against stored product pests. Plant compounds were added to feed disks composed of wheat flour and yeast and fed to the red flour bettle (Tribolium castaneum). By measuring insect mass, disk mass, and insect mortality over time it was possible to calculate a phagodepression index, an antifeedant index, the amount of treatment chemical ingested by the beetles, the mortality rate, and the efficiency of conversion of ingested food. The assay was performed for 60 hr to allow for possible habituation effects and to discriminate between phagodeterrency and physiological stress caused by treatments. - and -Pinene, eugenol, kaurenic acid, sparteine, essential oils ofMinthostachis mollis andMelaleuca quinquenervia, and extracts ofSapindus saponaria were tested. Using this assay we detected the presence of both phagodepressant and phagostimulant compounds inS. saponaria extracts, and we quantified the pronounced effects of sparteine onT. castaneum.     

Isolation,identification, and synthesis of sex pheromone components of female tea cluster caterpillar,Andraca bipunctata walker (Lepidoptera: Bombycidae) in Taiwan

Octadecanal (18:Ald), (E)-11-octadecenal (E11–18:Ald), (E)-14-octadecenal (E14–18:Ald) and (E,E)-11,14-octadecadienal (E11,E14–18:Ald) were isolated and identified as major components from the pheromone glands of the tea cluster caterpillar,Andraca bipunctata, in Taiwan by analyzing the mass spectra of gland components and their DMDS adducts. GC retention times and mass spectra of the components were in agreement with those of authentic synthetic compounds. The average amount of 18:Ald,E11–18:Ald,E14–18:Ald andE11,E14–18:Ald per female gland (1 to 3 days old) was 121±76, 50±20, 187±75, and 237±110 ng, respectively, in a ratio of 20:8:31:41. SyntheticE11,E14–18:Ald caught more males than each of the other three components or blank control in field trapping tests.E11,E14–18:Ald is reported as an insect sex pheromone for the first time. Male antenna responded toE11,E14–18:Ald strongly in an EAG analysis. Furthermore, 4 hr after the injection of PBAN (pheromone biosynthetic activating neuropeptide) into decapitated female moths (2 days old), the percentage of theE11,E14–C18 Ald in the gland extract increased from 0% to 75.5%, which was also significantly more than that of unligated and uninjected control at 55.1%. All these data indicated thatE11,E14–18:Ald is the sex pheromone of theAndraca bipunctata in Taiwan.     

Toxicity of linear furanocoumarins toSpodoptera exigua: Evidence for antagonistic interactions

The linear furanocoumarins psoralen, bergapten, and xanthotoxin were tested for toxicity to the beet armywormSpodoptera exigua (Hübner) under short ultraviolet (UVB) radiation. Increased dietary concentrations of each furanocoumarin significantly decreased insect larval weight, extended generation time, and induced higher mortality. Xanthotoxin was the most toxic, followed by psoralen and bergapten. Combining psoralen with bergapten, xanthotoxin, or both resulted in significantly antagonistic effects on insect mortality. The combination of bergapten and xanthotoxin, however, produced additive effects. The implications of these observations forS. exigua resistance in the wild plant accession ofApium prostratum and the enigma the findings represent for plant-insect relationships are discussed.     

Antitermitic Activities of Abietane-type Diterpenes from <Emphasis Type="Italic">Taxodium distichum</Emphasis> Cones

Eight known abietane-type diterpenes were isolated from the weak acidic fraction of the n-hexane extract from cones of Taxodium distichum, one of the extant, living fossil conifers. They were identified as 6,7-dehydroroyleanone (1), taxodal (2), taxodione (3), salvinolone (4), 14-deoxycoleon U (5), 5,6-dehydrosugiol (6), sandaracopimaric acid (7), and xanthoperol (8). The structures of these compounds were determined by comparison of NMR spectral data with published data. The antitermitic (termicidal and antifeedant) activities of the compounds 1–8 against the subterranean termite, Reticulitermes speratus Kolbe, were evaluated. Compounds 1 and 3 showed potent termicidal activity, and 5 and 8 showed potent antifeedant activity. Compound 1 was found to be one of the representative bioactive compounds in the n-hexane extract of T. distichum cones. Compounds 1–8, with the exception of 7, were oxides of ferruginol (9). Therefore, the presence of various oxidation forms of the abietane-type structure reflects their various bioactivities.     

Distribution and antifeedant associations of sesquiterpene lactones in cultivated sunflower (Helianthus annuus L.) on western corn rootworm (Diabrotica virgifera virgifera LeConte)

Seven antifeedant sesquiterpene lactones (STLs), 4,5-dihydroniveusin A, argophyllin B, argophyllin A, 15-hydroxy-3-dehydrodesoxytifruticin, niveusin B, 1,2-anhydridoniveusin A, and an unidentified epoxide, in cultivated sunflower (Helianthus annuus L.) have been quantified by a highperformance thin-layer chromatography and UV-reflectance scanning densitometry analysis. Age-related expression of STL content in sunflower reveals a heretofore undescribed pattern in which nonpolar STLs such as 15-hydroxy-3-dehydrodesoxytifruticin predominate up to an age of three weeks, but are subsequently displaced by polar STLs, especially argophyllin A, through later foliar stages and anthesis. This leaf pattern of STL ontogeny is maintained in three widely differentH. annuus cultivars (Giant Gray Stripe, Royal Hybrid 2141, Hybrid 7111), which in turn had similar total contents of STLs. Antifeedant activity for western corn rootworm was positively correlated with STL content, particularly with argophyllin A and its isomer argophyllin B, in respective tissue extracts. Enhanced amounts of highly antifeedant argophyllins, especially in newly grown leaf and floral tissues yielding sunflower progeny, strongly suggest that these epoxy-STLs are a chemical defense against insect herbivory.     

Interactions amongHeliothis virescens larvae,cotton condensed tannin and the CryIA(c) δ-endotoxin ofBacillus thuringiensis

The potential interactions among a plant-produced allelochemical, a phytophagous insect, and an endotoxin produced byBacillus thuringiensis were investigated using purified cotton condensed tannins, the CryIA(c)-endotoxin fromB. thuringiensis subsp.kurstaki strain HD-73, and larvae ofHeliothis virescens. Purified condensed tannin from cotton fed to neonateH. virescens reduced feeding and mortality caused by insecticidal crystals ofB. thuringiensis. In fifth instars, tannin reduced relative growth rate (RGR), relative consumption rate (RCR), but antagonized the effects of the crystal-endotoxin. Tannin did not deter feeding of fifth instars in choice tests with cellulose-ester disks. Masking tannin from interacting with the dietary ingredients of artificial diets and crystal protein by encapsulation in alginate gel suggested that tannin adversely affected feeding after ingestion.These results suggest that insect control tactics that employ-endotoxins in microbial insecticides and transgenic cotton plants may not be compatible when used in conjunction with plants containing high tannin concentrations.