Alleviation of α-tomatine-induced toxicity to the parasitoid,Hyposoter exiguae,by phytosterols in the diet of the host,Heliothis zea

The solitary, endoparasitic ichneumonid,Hyposoter exiguae (Viereck) is a parasitoid of the tomato fruitworm,Heliothis zea (Boddie). However, the parasitoid is deleteriously affected by the tomato glycoalkaloid, -tomatine, ingested from hosts (H. zea) fed on artificial diets or semipurified extracts of tomato plants that contained -tomatine. -Tomatine causes prolonged larval development; disruption or prevention of pupal eclosion; deformation of antennal, abdominal, and genital structures; and reduction in adult weight and longevity of the parasitoid. These toxic effects are exacerbated when the dietary dose of -tomatine is increased from 12 mol to 20 mol/g dry wt of diet. However, the toxicity of -tomatine is attenuated in parasitoids reared from hosts fed on artificial diets that contain equimolar or supramolar amounts of 3-OH-sterols admixed with -tomatine. Further, the toxicity of extracts from the foliage of different cultivars of tomatoes toH. exiguae is contingent upon the composite levels of -tomatine and total phytosterol (free and esterified). Cultivars with a low total sterol-tomatine ratio are more toxic toH. exiguae. The possible mode of action of -tomatine toxicity toH. exiguae by disruption of sterol metabolism is discussed.     

Enhancement of βα-recrystallization in β-form isotactic polypropylene during heating after roll deformation

Summary -form isotactic polypropylene shows -recrystallization behavior (recrystallization from - to -form) during slow heating. This is enhanced by deformation. -form specimen with uniaxially oriented lamellae was deformed by rolling, and -recrystallization was studied by DSC and x-ray diffraction. The result showed that (1) — recrystallization is promoted with the degree of deformation. (2) Deformed specimen shows -recrystallization from considerably low temperature compared with the undeformed one. (3) The recrystallized -form is c-axis-oriented along the roll direction. From these results the -recrystallization mechanism was discussed in view of -nucleus formation by deformation.     

Antifungal polyoxygenated fatty acids fromAeollanthus parvifolius

Two polyoxygenated fatty acids with antifungal activity have been isolated from aerial parts ofAeollanthus parvifolius (Labiatae) using bioassay-guided isolation procedures. Spectroscopic analysis was used to identify the compounds as (Z)-4,9-diacetoxy-6,7-epoxy-5-hydroxy-8-oxododeca-2-enoic acid and (Z)-4,6,7,9-tetraacetoxy-5-hydroxy-8-oxododeca-2-enoic acid. Both of these compounds inhibited spore germination ofCladosporium cucumerinum. Minimum inhibitory doses were 1 µg and 5 µg, respectively, but only the former inhibited germination ofAspergillus niger at a dose of 5 µg. Neither compound exhibited antibacterial activity. (Z)-4,9-Diacetoxy-6,7-epoxy-5-hydroxy-8-oxododeca-2-enoic acid reduced the hyphal growth ofPythium ultimum. The mode of action was not resolved but did not involve either the disruption of the cell wall membrane or the inhibition of extracellular enzymes. Application of (Z)-4,6,7,9-tetraacetoxy-5-hydroxy-8-oxododeca-2-enoic acid to seedling plants did not give any protection against fungal attack, and indeed the compound appeared to be phytotoxic.     

Determination of the enantiomeric composition of several insect pheromone alcohols

Details are given for the determination of the enantiomeric composition of several insect pheromone alcohols. The two methods used in the determination were: formation of the derivative with (+)--methoxy--trifluoromethylphenylacetyl chloride and the use of chiral lanthanide shift reagents. The five alcohols studied and their enantiomeric compositions are: sulcatol fromGnathotrichus sulcatus 6535 (+)/(–),trans-verbenol fromDendroctonus frontalis 6040 (+)/(–), 4-methyl-3-heptanol fromScolytus multistriatus 100% (–), seudenol fromDendroctonus pseudotsugae 5050 (+)/(–), and ipsdienol fromIps pini (Idaho) 100% (–). Determinations were done on 50–500 g substrate.     

Differential metabolism of 1,8-cineole in insects

In order to compare the metabolism of 1,8-cineole in the pyrgo beetle, Paropsisterna tigrina, three other herbivorous insect species, Faex nigroconspersa, Chrysophtharta bimaculata, and Oxyops vitiosa, were fed 1,8-cineole leaf diets. F. nigroconspersa adults excreted predominantly 9-hydroxy-1,8-cineole (36.2% of the volatile constituents) with some 2-hydroxy-1,8-cineole (11.4%). In contrast, larvae excreted predominantly 2-hydroxy-1,8-cineole (27.4%) and smaller proportions of 9-hydroxy-1,8-cineole (5.2%) and 3-hydroxy-1,8-cineole (4.3%). C. bimaculata adults excreted predominantly 3-hydroxy-1,8-cineole (16.5%). Oxyops vitiosa adults, on a lower 1,8-cineole diet, excreted predominantly 2,9-dihydroxy-1,8-cineole (4.2%) and 2-hydroxy-1,8-cineole (3.5%), with smaller proportions of 3-hydroxy-1,8-cineole (1.1%) and 9-hydroxy-1,8-cineole (0.5%). This is the first reported occurrence of a dihydroxycineole as an insect metabolite. Gas chromatographic and mass spectral data for hydroxycineoles are recorded and interspecific metabolite variation discussed.     

Occurrence and Correlations of Monoterpene Hydrocarbon Enantiomers in Pinus sylvestris and Picea abies

The relative amounts and enantiomeric compositions of monoterpene hydrocarbons in branch and trunk xylem, in needles, and in resin from apical buds in 18 Pinus sylvestris trees have been determined and compared with the terpene content in branch xylem and needles of Picea abies. Besides the high amount of (+)-3-carene, an excess of (+)--pinene has been found in P. sylvestris, whereas in P. abies (–)--pinene dominates over (+)--pinene. In P. sylvestris, clear positive correlations were found between (+)--pinene and (+)-camphene in the four tissues analyzed. Good positive correlations were also observed between (–)--pinene and (–)-camphene in the two types of xylem, between (+)--pinene and (+)--pinene in the resin, and between tricyclene and (–)-camphene in resin and needles. In P. abies, positive correlations were found between (+)--pinene and (+)-camphene in the branch xylem and between tricyclene and (–)-camphene as well as between (–)--pinene and (–)-camphene in the needles. Complex relationships between (–)--pinene and (–)--pinene were found both in the P. abies and in the P. sylvestris tissues. The importance of the enantiomeric composition of -pinene for the host selection of Ips typographus, Tomicus piniperda, and Hylobius abietis is discussed.     

Isolation and identification of male medfly attractive components inLitchi chinensis stems andFicus spp. stem exudates

Short-range attraction/feeding stimulation of male Mediterranean fruit flies [Ceratitis capitata (Wiedemann), (Diptera: Tephritidae)] to a stem extract of a host plant,Litchi chinensis Sonn. (Sapindaceae), and to milky exudates from stems of nonhost plants,Ficus retusa L. andF. benjamina L. (Moraceae), were attributed to the presence of the sesquiterpene -copaene. The presence of -copaene in the milky exudate from stems ofF. benghalensis L. is also suggested as eliciting similar behavioral responses in male medflies. The presence of minor quantities of -ylangene in the plants and its contributory effects to the behavioral response of male medflies is discussed. Short-range attraction/feeding stimulation of male medflies to equal amounts of -ylangene-free -copaene samples (94.5%+), prepared from -copaene-enriched angelica seed oil and copaiba oil, respectively, showed no difference in intensity of response. -Ylangene elicited a slightly less intense response for male medflies than -copaene.Names of products in this paper are included for the benefit of the reader and do not imply endorsement or preferential treatment by USDA.     

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.     

Behavioral and neurosensory responses of the boll weevil,Anthonomus grandis Boh. (Coleoptera: Curculionidae), to fluorinated analogs of aldehyde components of its pheromone

Competitive field tests with -fluorinated analogs of compounds III and IV (III--F and IV--F, respectively) of the boll weevil,Anthonomus grandis Boh., aggregation pheromone showed these compounds, when combined with the other pheromone components [(±)-I and II], to be as attractive as grandlure [(+)-I, II, and III+IV]. Dose-response curves constructed from electroantennograms of male boll weevils to serial stimulus loads of III, IV, III--F, IV--F, and the corresponding acyl fluorinated analogs (III-acyl-F and IV-acyl-F) showed the -fiuorinated analogs to be as active as the pheromone components (threshold=0.1 g), while the acyl fluorinated analogs had a 10-100 x higher threshold (=1-10 g). Single-neuron recordings showed that IV neurons and II neurons (Dickens, 1990) responded to IV--F and III--F, respectively, while IV-acyl-F and III-acyl-F were inactive. Since a previous study showed compounds I, II, and IV to be essential for behavioral responses in the field, it seems likely that the activity of the -fluorinated analogs observed here is due to the stimulation of IV neurons by IV--F as indicated in single neuron recordings.     

Response ofScolytus multistriatus (Coleoptera: Scolytidae) to α- and δ-multistriatin in Switzerland

Laboratory bioassays and field tests demonstrated that a Swiss population ofS. multistriatus responded much more strongly to - than to -miltistriatin in combination with 4-methyl-3-heptanol and -cubebene. High concentrations of brevicomin appeared to replace -multistriatin in evoking a response byScolytus species, but this effect can be explained by the fact that the brevicomin was contiminated with small amounts of -multistriatin. Frontalin, another bicyclic ketal, showed no biological activity. Field tests indicated thatS. pygmaeus aggregates to the same attractant mixture asS. multistriatus. S. scolytus also responded preferentially to this mixture, but the relative amounts of -multistriatin to 4-methyl-3-heptanol do not appear to be as important as forS. multistriatus.     

Comparative effects of two plant secondary metabolites on host-parasitoid association

Two plant-derived allelochemicals, berberine and -terthienyl (- T), were tested for their effects on the European corn borer,Ostrinia nubilalis, and its endoparasitoidDiadegma terebrans. The compounds were administered to the host insect in meridic diets, and the responses of the host larvae and parasitoids reared from treated hosts were measured in terms of growth parameters and survival. InO. nubilalis, survival to pupation and adult emergence were reduced significantly by the inclusion of berberine and -T in larval diets at a concentration of 100 g/g. However, in the parasitoid, adverse effects were much more apparent with the -T treatment than with the berberine treatment. -T and one of its metabolites were found in host larvae and in emerged adult parasitoids and their cocoons. Berberine residues were not detected. The implications of these responses to compounds of widely differing physiological properties are discussed with reference to host-plant resistance and biological control.     

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.     

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.     

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.     

Comparison of Oligosaccharide Compositions in Male Nuptial Secretions of Three Cockroach Species of the Genus Blattella

Male cockroaches of the genus Blattella secrete courtshippheromones from abdominal tergal glands. Conspecific females mount courting males and feed on their tergal exudates. In the German cockroach, B. germanica, a complex mixture of oligosaccharides was previously identified as the major phagostimulants in the male tergal secretion. We compared the oligosaccharide compositions of three Blattella species from different habitats, B. germanica (house), B. lituricollis (field), and B. nipponica (forest), by gas chromatographic (GC) analysis of their trifluoroacetylated derivatives. The three possessed a series of maltooligosaccharides and oligoglucosyl trehaloses with 14 and 11 linkages in common. However, B. germanica was conspicuous for its accumulation of a oligoglucosyl trehalose with a 16 linkage [O--D-glucopyranosyl-(16)--D-glucopyranosyl -D-glucopyranoside] as the most prominent component of the secretion. Such diversification of the male pheromonal compositions within the genus might be reflected by biosynthetic systems in males and chemosensory properties in females suited for their natural habitat.     

Identification and field testing of female-produced sex pheromone components of the spring cankerworm,Paleacrita vernata Peck (Lepidoptera: Geometridae)

Two sex pheromone components, 3(Z),6(Z),9(Z)-nonadecatriene (3Z,6Z,9Z-19 H), and 3(Z),6(Z),9(Z)-eicosatriene (3Z,6Z,9Z-20 H), have been positively identified, and a third component, 6(Z),9(Z)-nonadecadiene (6(Z),9(Z)-19 H) has been tentatively identified from abdominal tip extracts of female spring cankerworm moths,Paleacrita vernata Peck (Lepidoptera Geometridae). The pheromone components were identified by a combination of gas chromatography, electroantennography, mass spectrometry, chemical tests, comparison with standards, and field testing. Only 3Z,6Z,9Z-20 H exhibited significant attractant activity when tested alone, and it was potentiated by the other two components. The attractive blend was an 821 ratio of 3Z,6Z,9Z-20H/3Z,6Z,9Z-19H/6Z,9Z-19H. However, the two-component blend of 3Z,6Z,9Z-20 H and 6Z,9Z-19 H (81 ratio) was as attractive as the three-component blend in further field tests. A series of related compounds, the diene monoepoxides available from epoxidation of C₁₉ and C₂₀ 3Z,6Z,9Z-trienes, some of which have been found in the pheromone blends of other moth species, were tested as behavioral antagonists. The attraction of male moths to synthetic lures was suppressed by the addition of 6Z,9Z-cis-3,4-epoxy-nonadecadiene to the lures. Additional experiments were performed to determine the effects of lure dosage, trap height, and trap design on the numbers of male moths captured.Issued as NRCC 30711.     

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.     

A four-component pheromone blend for optimum attraction of redbacked cutworm males,Euxoa ochrogaster (Guenée)

Four acetates,Z-5-decenyl acetate,Z-5-,Z-7-, andZ-9-dodecenyl acetates, in microgram ratios of 120021 or 120062 were excellent, specific sex pheromone blends for capturing male redbacked cutworm moths in cone traps. Blends in ratios of 120021 and 220021 at 1000 g/ rubber septum dispenser remained highly effective for 6 weeks under field conditions. The essential minor components,Z-5-decenyl,Z-7-, andZ-9-dodecenyl acetates, became inhibitory at concentrations of about 10% in the blends, and this may be an important general phenomenon in lepidopteran pheromones. Blends involving a parapheromone,Z-5-undecenyl acetate, withZ-5-,Z-7-, andZ-9-dodecenyl acetate, in microgram ratios of 820021 or 2020062 were also excellent specific attractants for this species. TheZ-8-dodecenyl acetate had no obvious effect on the attraction of the redbacked cutworm males.     

Interspecific variation in defense secretions of malaysian termites from the genusNasutitermes (Isoptera,nasutitermitinae)

The defense secretions of five species of MalaysianNasutitermes,N. longinasus, N. matangensis, N, havilandi, N. johoricus, andNasutitermes species 01, are compared.N. longinasus andN. species 01 provide trinervitene alcohols,N. havilandi mainly tricyclic trinervitene and tetracyclic kempane alcohols and acetates, whereasN. matangensis furnish acetyl/propionyl derivatives of trinervita-11(12),15(17)-dien-3,9,13-triol (XXI and XXII). A new diterpene, assigned as trinervita-11(12),15(17)-dien-3,13-diol-3,13-O-diacetate (XVII), is isolated fromN. havilandi. The mono- and diterpenoid compositions, being species-specific, are useful for chemotaxonomic and phylogenetic studies.     

Sex pheromone of the chokecherry leafroller moth,Sparganothis directana

(E)-9,11-Dodecadienyl acetate and (Z)-9,11-dodecadienyl acetate in conjunction with (E)-11-tetradecenyl acetate and (Z)-11-tetradecenyl acetate were found to comprise the sex pheromone ofSparganothis directana, based on chemical analysis, electroantennogram tests, and field trapping. (E)-9-Dodecenyl acetate and (Z)-9-dodecenyl acetate were also found in gland extracts but did not influence trap catches. The relative amounts of these compounds in the gland were 3521928 106, in the order named. Only (E)-9,1 1-dodecadienyl acetate, (E)-11-tetradecenyl acetate, and (Z)-11-tetradecenyl acetate were required for attraction of males to traps, dispensed in the relative amounts 501238, respectively.Lepidoptera: Tortricidae.Supported by National Science Foundation grant PCM 78-13241.