Electroantennographic and coupled gas chromatographic-electroantennographic responses of the mediterranean fruit fly,Ceratitis capitata,to male-produced volatiles and mango odor

We have identified five compounds from the headspace of calling male Mediterranean fruit flies (medfly),Ceratitis capitata (Wiedemann), and three compounds from the headspace of ripe mango (Mangifera indica L). using coupled gas chromatographic-electroantennographic (GC-EAG) recordings, coupled gas chromatographic-mass spectrometric (GC-MS) analysis, and electroantennographic (EAG) assays of standards. The male-produced volatiles eliciting responses from female antennae were ethyl-(E)-3-octenoate, geranyl acetate, (E,E)--farnesene, linalool, and indole. An EAG dose-response test of linalool enantiomers and indole with female medfly antennae showed relatively strong EAG activities, but no significant difference between (R)-(-)-linalool and (S)-(+)-linalool. The three mango volatiles were identified as (1S)-(-)--pinene, ethyl octanoate, and-caryophyllene. In addition, a strong antennal response was recorded from a contaminant,-copaene, present in a commercial sample of-caryophyllene. The EAG response amplitudes from both male and female antennae to the above three mango volatiles were significantly greater than to a hexanol control. For both male and female medfly antennae, the greatest EAG responses were elicited by-caryophyllene followed by ethyl octanoate. The mean EAG responses of female antennae to-caryophyllene and (1S)-(-)--pinene were significantly greater than those of male antennae.     

Identification and Distribution of Oviposition Stimulants for Monarch Butterflies in Hosts and Nonhosts

Flavonol glycosides that act as oviposition stimulants for monarch butterflies were surveyed from a range of asclepiad hosts and some nonhosts. Major stimulants also were identified as quercetin-3-O-(2-O--xylosyl)--D-galactoside and quercetin-3-O--D-galactoside from Asclepias syriaca and A. incarnata, respectively. The flavonol glycosides in A. curassavica, A. tuberosa, A. incarnata, A. syriaca, A. humistrata, A. albicans, A. eriocarpa, Calotropis procera, Cynanchum acutum, Vincetoxicum (Cynanchum) nigrum and in nonhosts Hoya australis and Nerium oleander were compared and characterized by HPLC and spectral studies. There was great variation in quercetin glycoside content. On the basis of the sugar moieties attached to quercetin, the asclepiad glycosides were classified broadly as those containing: (1) galactose, glucose, and rhamnose; (2) galactose, glucose, and xylose; and (3) galactose, glucose, xylose, and rhamnose. In most cases, galactose was attached to the 3-O-position (1) of quercetin and other sugars were attached either to the 2 or 6 position of galactose. The sugars of triglycosides were attached at both 2 and 6 positions. A geographical pattern of flavonol distribution that may have affected the evolution of host recognition by the butterflies is suggested.     

Seasonal variation of lipids in femoral gland secretions of male green iguanas (Iguana iguana)

Femoral gland secretions were collected from 21 captive adult male green iguanas (Iguana iguana) in Orotina, Costa Rica, and San Diego, California, during the breeding (November) and nonbreeding (March) seasons. Lipids were extracted with methylene chloride, weighed, separated by thin-layer chromatography, and analyzed by gas chromatography-mass spectrometry. Free and esterified C₁₄-C₂₆ fatty acids, 5-cholestan-3-ol (epico-prostanol), cholest-5-en-3-ol (cholesterol), cholest-5-en-24-methyl-3-ol (campesterol), cholesta-5,22-dien-24b-ethyl-3-ol (stigmasterol), cholesta-8,24(5)-dien-4,4,14-trimethyl-3-ol (lanosterol), cholest-5-en-24-ethyl-3-ol (-sitosterol), and two uncharacterized sterols were indicated. More lipids were recovered from femoral gland secretions obtained during the breeding than the nonbreeding months, indicating that secretion deposits may be more detectable during the mating season.     

Variation in aphid alarm pheromone content among glandular and eglandular-hairedMedicago accessions

Pea (Acyrthosiphon pisum Harris) and blue alfalfa aphid (A. kondoi Shinji) deterrency in alfalfa (Medicago saliva L.) may result from incorporating higher levels of the aphid alarm pheromone,(E)--farnesene relative to(E)--caryophyllene. We evaluated five eglandular and two glandular-haired alfalfa accessions for differences in(E)--farnesene and(E)--caryophyllene content under glasshouse conditions using supercritical fluid extraction and gas chromatography. In addition, pea and blue alfalfa aphid olfactory behavioral tests were conducted uponMedicago species containing different ratios of(E)--famesene relative to(E)--caryophyllene. No differences in(E)--caryophyllene content were observed among the seven entries (=0.42 ng/g plant material). Significant differences (P 0.05) among entries were observed for(E)--famesene content, with KS94GH6 exhibiting the highest (1.18 ng/g), and CUF 101 the lowest levels (0.35 ng/g). Elite tetraploid sources possessed significantly lower levels (=0.42 ng/g) of(E)--farnesene than did wild and cultivated diploid accessions (=0.83 ng/g). Olfactory behavioral tests for both the pea and blue alfalfa aphids demonstrated KS94GH6 repelled aphids while cultivated alfalfa types attracted aphids in each case. Previously demonstrated aphid resistance in diploid KS94GH6 may result from superior(E)-- farnesene levels, but(E)--farnesene is probably not a factor in cultivated alfalfa resistance. Finally, accession KS94GH6 could act as an excellent germplasm resource for the incorporation of higher(E)--farnesene levels into cultivated alfalfa.Research supported by the New Mexico State University Agricultural Experiment Station.     

Soldier defense secretions of malaysian free-ranging termite of the genusLacessititermes (Isoptera,Nasutitermitinae)

Soldiers of free-ranging termites of the genusLacessititermes (Isoptera, Nasutitermitinae) secrete from their frontal glands a mixture of monoterpenes, sesquiterpenes, and diterpenes.Lacessititermes ransoneti, L. laborator, andL. species A produce species-specific secretions, the composition being most complex forL. laborator. Apart from known mono- and dihydroxytrinervitadienes, the following new diterpenes were isolated and tentatively assigned as trinervita-1(15),8(19)-dien-2,3,9,14-tetraol 2,3,14-O-triacetate, trinervita-1(15),8(19)-dien-2,3,9,14-tetraol 2,3,14-O-triacetate, 2,3,9, 14-tetraacetoxy-1 (15), 8(19)-trinervitadiene, and 2,3,11,13-tetraacetoxy-1(15),8(19)-trinervitadiene. Data on intragenus chemical variations were subjected to canonical discriminant analysis and genetic distances among the species were calculated to depict intragenus identities and affinities.     

Antifungal Activity of Some B,D-Seco Limonoids from Two Meliaceous Plants

Isolation and characterization of B,D-seco limonoids from Swietenia mahogani have been described. Seven limonoids from S. mahogani and five limonoids from Khaya senegalensis were tested for antifungal activity against the groundnut rust Puccinia arachidis. Mexicanolide, 3-acetoxy-mexicanolide, 3-hydroxymexicanolide, 2,3-dihydroxymexicanolide from K. senegalensis, and 6-acetylswietenine and 6-acetyl-3-tigloylswietenolide from S. mahogani effectively reduced the number of rust pustules on detached groundnut leaves. Possible correlation of structure to antifungal activity is discussed.     

Investigation of the role of diterpenes produced by marine pulmonatesTrimusculus reticulatus andT. conica

The intertidal pulmonate limpetTrimusculus reticulatus, which is found in caves or crevices along the California coast, was previously reported to contain two novel diterpenoids, 6-isovaleroxylabda-8,13-dien-7,15-diol (1) and 2,7-diacetoxy-6-isovaleroxylabda-8,13-dien-15-ol (2). Dissection of the animals prior to extraction revealed that the diterpenoids were concentrated in the mantle, foot, and mucus, but not in the viscera. The presence ofT. reticulatus or its mucus was toxic to veliger larvae of the sabellariid reef-building tube wormPhragmatopoma californica. The major diterpenoid1 was responsible for the observed larvicidal activity. Protection against overgrowth by settling invertebrate larvae is important for the survival of this sessile filter-feeding pulmonate. A related pulmonate,T. conica, which was found in similar intertidal habitats in New Zealand, contained 6-acetoxy-7-isovaleroxylabda-8,13-dien-15-oic acid (3) and 1,7,12,18-tetraacetoxy-cholest-5-en-3-ol (4). The diterpene3 was also localized in the foot, mantle, and mucus ofT. conica but was not larvicidal toP. californica.     

Leaf surface chemicals fromNicotiana affecting germination ofPeronospora tabacina (adam) sporangia

A bioassay was used to evaluate the effects of cuticular leaf components, isolated fromN. tabacum, N. glutinosa (accessions 24 and 24a), and 23other Nicotiana species, on germinationof P. tabacina (blue mold). The leaf surface compounds included- and-4,8,13,-duvatriene-l,3-diols (DVT-diols), (13-E)-labda-13-ene-8-,15-diol (labdenediol), (12-Z)-labda-12,14-diene-8-ol (cis-abienol), (13-R)-labda-8,14-diene-13-ol (manool), 2-hydroxymanool, a mixture of (13-R)-labda-14-ene-8,13-diol (sclareol), and (13-S)-labda-14-ene-8,13-diol (episclareol), and various glucose and/or sucrose ester isolates. The above in acetone were applied onto leaf disks of the blue moldsusceptibleN. tabacum cv. TI 1406, which was then inoculated with blue mold sporangia. Estimated IC₅₀ values (inhibitory concentration) were 3.0g/cm² for-DVT-diol, 2.9/cm² for-DVT-diol, 0.4g/cm² for labdenediol and 4.7g/cm² for the sclareol mixture. Manool, 2-hydroxymanool, andcis-abienol at application rates up to 30g/cm² had little or no effect on sporangium germination. Glucose and/or sucrose ester isolates from the cuticular leaf extracts of 23Nicotiana species and three different fractions fromN. bigelovii were also evaluated for antimicrobial activity at a concentration of 30g/cm². Germination was inhibited by >20% when exposed to sugar esters isolated fromN. acuminata, N. benthamiana, N. attenuata, N. clevelandii, andN. miersii, and accessions 10 and 12 ofN. bigelovii. These results imply that a number of compounds may influence resistance to blue mold in tobacco.     

Specific features of the phase transformations occurring during the sintering process of the beta-alumina based ceramics and their properties

Conclusions During the sintering process of beta-alumina obtained using the method of plasmochemical synthesis, the structural transformation occurs and it is accompanied by the separation of the excess Na₂O and the formation of an intergranular meltlike phase that is saturated with sodium and is characterized by high dielectric properties.The quantity of the meltlike phase and the magnitude of the /( + ) ratio determine the degree of stabilization (stability) and the final resistivity of the material and depend on the initial chemical composition and the heating rate maintained during the sintering process.It was shown that when the duration of residence of the material in the hot zone of the furnace is increased or when the specimens sintered maintaining high heating rates are subjected to additional heat treatment, one observes the occurrance of the reverse structural transformation that is characterized by an increase of the phase ratio /( + ) 1, a reduction in the quantity of the meltlike phase right up to its complete disappearance, and a decrease of the electrical resistivity of the material.In the materials having a large excess quantity of sodium oxide, the process of crystallization of the intergranular NaAlO₂ phase occurs simultaneously with the second phase transformation.The best ceramic and electrophysical parameters were obtained when sintering the material contained 7.9% Na₂O.Translated from Ogneupory, No. 3, pp. 13–18, March, 1990.     

Aggregation arrestant pheromone of the German cockroach,Blattella germanica (L.) (Dictyoptera: Blattellidae): Isolation and structure elucidation of blattellastanoside-A and -B

The aggregation pheromone of the German cockroach,Blattella germanica, consists of attractant and arrestant, which can be detected by olfactometer and choice-chamber assay, respectively. Both were extracted from the frass-contaminated filter paper being used as a shelter. They were separated by solvent partition withn-butanol and water. The arrestant from then-butanol phase was purified by open column chromatography and then successive HPLC isolated two major arrestant components. Spectral evidence from SI-MS, HR-EI-MS, and NMR experiments with pulse techniques provided possible structures as 1-(6-chloro-4,5-epoxy-5-stigmast-3-yl)--d-glucopyranoside and 1-(6-chloro-5-hydroxy-5-stigmast-3-yl)--d-glu-copyranoside, denoted as blattellastanoside-A and blattellastanoside-B, respectively. They represented arrestant activity as median effective doses (ED₅₀) at 0.044 (A) and 3.2 (B) nmol on 1.0 cm² of Whatman No. 1 filter paper.     

Identification and Function of Prothoracic Exocrine Gland Steroids of the Dytiscid Beetles Graphoderus cinereus and Laccophilus minutus

The chemical composition of the prothoracic defensive secretion of the water beetles Graphoderus cinereus and Laccophilus minutus was examined by gas chromatographic–mass spectrometric analysis of trimethylsilylated gland extracts. The main components are 3,11-dihydroxy-5-pregnan-20-one in G. cinereus and 3,12-dihydroxy-5-pregnan20-one in L. minutus. Fully saturated pregnanes have not been found in the prothoracic defensive glands of dytiscids before. Based on tests with synthetic compounds, their biological role was examined in a feeding assay with the minnow Phoxinus phoxinus. Agar pellets containing either steroid strongly deterred feeding.     

Defensive steroids from a carrion beetle (Silpha novaboracensis)

Two novel steroids, 3,7-dihydroxy-14-pregn-4-en-15,20-dione (1) and 3,7, 20-trihydroxy-14-pregn-4-en-15-one (4), have been characterized from the rectal gland ofSilpha novaboracensis (Coleoptera: Silphidae). Judging from the function of comparable pregnanes in another species ofSilpha, the compounds may play an antipredator role.Paper No. 81 of the seriesDefense Mechanisms of Arthropods. Paper No. 80 is Eisner, T., Deyrup, M., Jacobs, R., and Meinwald, J.,J. Chem. Ecol. 12:1407–1415.     

Larval osmeterial secretions of the swallowtails (Papilio)

The larval osmeterial secretions of sixPapilio species examined displayed a remarkable qualitative change at the fourth larval ecdysis. The secretions of 4th (penultimate) instar larvae ofP. machaon, P. memnon, P. helenus, P. bianor, andP. maackii principally comprised mono- and/or sesquiterpenoids. The compounds identified from these species included -pinene, sabinene, -myrcene, limonene, -phellandrene, (Z)--ocimene, (E)--ocimene, -elemene, -caryophyllene, (E)--farnesene, -selinene, (E,E)--farnesene, germacrene-A, germacrene-B, caryophyllene oxide, methyl 3-hydroxy-n-butyrate, and acetic acid. In contrast, the secretion of 4th larval instar ofP. xuthus, although containing similar terpenic compounds, was accompanied by large amounts of aliphatic acids and their esters: isobutyric acid, 2-methylbutyric acid, methyl isobutyrate and methyl 2-methylbutyrate. On the other hand, the osmeterial secretions of 5th (last) instar larvae varied little in quality among the six species, and the identified compounds consisted of isobutyric acid, 2-methylbutyric acid, methyl isobutyrate, ethyl isobutyrate, methyl 2-methylbutyrate, ethyl 2-methylbutyrate, and isovaleric acid, the last of which was specific toP. bianor andP. maackii. The chemical alteration of osmeterial exudate synchronized at the final larval ecdysis with the larval morphological change (particularly in body coloration) that appears to be of defensive significance against predators.     

Corn volatiles as attractants for northern and western corn rootworm beetles (Coleoptera: Chrysomelidae:Diabrotica spp.)

Synthetic corn volatiles and selected analogs were tested in commercial corn fields for attractiveness to feral northern (NCR,Diabrotica barberi) and western corn rootworm beetles (WCR,D. virgifera virgifera). Two new attractants, geranylacetone and -terpineol, were identified among corn terpenes and compared at four stages in crop development with the phenylpropanoid standards cinnamyl alcohol and 4-methoxy-cinnamaldehyde, with each component at 30 mg/trap. Dose-response relationships (0.1–100 mg/trap) and efficacy of two-component blends (30 mg/component) were also examined. More beetles were captured on traps baited with (+)- than (–)--terpineol, but the difference was statistically significant only for WCR. Captures with geranylacetone or (+)--terpineol were directly proportional to the logarithm of the attractant dose. WCR females were attracted to as little as 0.1 mg of either compound. WCR males required 1.0 mg of (+)--terpineol and were not attracted to geranylacetone at any dose. NCR required 0.3 mg of either attractant and showed less marked response differences between the sexes than did WCR. Geranylacetone and cinnamyl alcohol were equally effective attractants, whereas (+)--terpineol was significantly less attractive to WCR but more attractive to NCR than was 4-methoxycinnamaldehyde. Corn terpenes and phenylpropanoid standards produced similar seasonal response patterns in that captures tended to rise in each case as the season progressed, except during silking when no compound was attractive. Mixing corn terpenes or phenylpropanoid standards synergized responses of WCR females, but (+)--terpineol suppressed attraction of NCR females to geranylacetone.Mention of a proprietary product or company name does not imply endorsement by the U.S. Department of Agriculture.     

Ethyl m-Digallate from Red Maple, Acer rubrum L., as the Major Resistance Factor to Forest Tent Caterpillar, Malacosoma disstria Hbn.

An ethanolic extract of red maple (Acer rubrum L.) leaves (RME) applied to trembling aspen (Populus tremuloides Michx.) leaves reduced feeding in choice test assays with forest tent caterpillar larvae (Malacosoma disstria Hbn.) (FTC), whereas a trembling aspen foliage extract, similarly applied, stimulated feeding. Compounds isolated from the RME were gallic acid, methyl gallate, ethyl gallate, m-digallate, ethyl m-digallate, 1-O-galloyl--D-glucose, 1-O-galloyl--L-rhamnose, kaempferol 3-O--D-glucoside, kaempferol 3-O--D-galactoside, kaempferol 3-O--L-rhamnoside, kaempferol-3-O-rhamnoglucoside, quercetin 3-O--D-glucoside, quercetin 3-O--L-rhamnoside and quercetin 3-O-rhamnoglucoside, (–)-epicatechin, (+)-catechin and ellagic acid. All of the gallates, (–)-epicatechin, and kaempferol 3-O--L-rhamnoside deterred feeding on trembling aspen leaf disks when applied at 0.28 mg/cm². The two digallates deterred feeding by 90% and were the most effective. HPLC analysis indicated that ethyl m-digallate is present in amounts 10–100 × higher in RME (2.5–250 mg/g) than any other compound. Thus, ethyl m-digallate appears to be the major compound protecting red maple from feeding by FTC, with a minor contribution from other gallates.     

Musk deer (Moschus moschiferus): Reinvestigation of main lipid components from preputial gland secretion

The qualitative and quantitative composition of the principal lipid constituents of Siberian musk deer (Moschus moschiferus) preputial gland secretion, main odor carriers and potential precursors of odorous substances, was investigated by means of high-performance liquid chromatography. Free fatty acids and phenols (10%), waxes (38%), and steroids (38%) were found to be the main groups of the secretion lipids. Cholestanol (I), cholesterol (II), androsterone (III), ⁴-3-hydroxy-17-ketoandrostene (IV), 5, 3-hydroxy-17-ketoandrostane (V), 5, 3, 17-dihydroxyandrostane (VI), 5, 3, 17-dihydroxyandrostane (VII), and 5, 3, 17-dihydroxyandrostane (VIII) were isolated from the steroid fraction and their structures confirmed by IR, PMR, and mass spectra. 3-Methylpentadecanone (muscone) was not identified among the secretion lipids. Preputial gland secretion stimulated sex behavior of musk deer females.     

Correspondence of soldier defense secretion mixtures with cuticular hydrocarbon phenotypes for chemotaxonomy of the termite genus Reticulitermes in North America

Soldier defense secretions from samples of Reticulitermes collected in California, Nevada, Arizona, New Mexico, and Georgia were characterized and correlated with cuticular hydrocarbon phenotypes. Twenty-seven cuticular hydrocarbon phenotypes have been defined, and soldier defense secretion (SDS) phenotypes have been described for 25 of these. Forty-five terpenoid compounds were found, including monoterpenes, sesquiterpenes, and a few diterpenes. The monoterpenes include (–)--pinene, (–)--pinene, (–)-camphene, myrcene, (Z)- and (E)-ocimene, and (–)-limonene. The major sesquiterpenes produced are (+)--cadinene, (+)--cadinene aldehyde, (–)-germacrene A, germacrene B, -himachalene, and -bisabolene. Some SDS phenotypes pair with more than one cuticular hydrocarbon phenotype; however, with two exceptions, each hydrocarbon phenotype is associated with only one SDS phenotype. These chemical characterizations lend support to the conclusion that there are numerous undescribed species of Reticulitermes in North America.     

Inhibition of β-Glucosidase and Esterase by Tannins from Betula, Salix, and Pinus Species

The reaction of tannin fractions isolated from the bark of Betula, Salix, and Pinus species with two enzymes, -glucosidase and esterase, was investigated. The influence of precipitation to the hydrolytic capacity of -glucosidase also was studied. All tannins studied precipitated -glucosidase and esterase, and moderate differences in the precipitating capacities of the tannins were observed. Interestingly, complex formation between -glucosidase and tannin did not markedly affect the activity of the enzyme. Therefore, complex formation during the insect/herbivore feeding does not necessarily change the defense activity of phenolic glycosides or decrease activity of digestive enzymes.     

Additional male mediterranean fruitfly (Ceratitis capitata wied.) Attractants from Angelica seed oil (Angelica archangelica L.)

Two sesquiterpene hydrocarbons, -copaene and -ylangene, were isolated from bioactive fractions of angelica seed oil and were shown by field bioassays to be attractive to the male Mediterranean fruit fly. Their relative attractiveness, compared with the(+)-and (–)--copaene enantiomers, are: (+)--copaene>angelica -copaene>angelica -ylangene>(–)--copaene. The enantiomer ratios for the two compounds are: -copaene, 61.4% (+), 38.6% (–); -ylangene, 91.9% (+), 8.1% (–).trans--Bergamotene was also isolated from the same fractions, but in sufficient quantity for bioassay [enantiomer ratio: 95.7% (+), 4.3% (–)].     

Orientation of boll weevil,Anthonomus grandis boh. (Coleoptera: Curculionidae), to pheromone and volatile host compound in the laboratory

Behavioral responses of male and female boll weevils to the aggregation pheromone, grandlure, and the major volatile of cotton, -bisabolol, were investigated using a new dual-choice olfactometer. Dosage-response experiments revealed both males and females to be attracted by the aggregation pheromone at the 1.0 g dosage. However, only males were attracted to -bisabolol (1.0 g). Both sexes were repelled by the highest dosage of-bisabolol tested (10 g). In preference experiment, males chose grandlure over -bisabolol, while both sexes chose the combination of grandlure + -bisabolol over -bisabolol alone. There was some evidence for synergism between pheromone and plant odor for the females. The results correlate well with previous electrophysiological and behavioral experiments.Mention of a trademark, proprietary product, or vendor does not constitute a guarantee or warranty of the product by the U.S. Department of Agriculture and does not imply its approval to the exclusion of other products or vendors that may also be suitable.