Sex pheromone of aPlanotortrix excessana sibling species and reinvestigation of related species

The sex pheromone of aPlanotortrix excessana sibling species was investigated. Females were found to produce eight potential pheromone components: dodecyl acetate, tetradecyl acetate (14OAc). (Z)-5-tetradecenyl acetate (Z5-14OAc), (Z)-7-tetradecenyl acetate (Z7-14OAc), (Z)-9-tetradecenyl acetate, hexadecyl acetate, (Z)-7-hexadecenyl acetate, and (Z)-9-hexadecenyl acetate. When these compounds were bioassayed using field-trapping and wind-tunnel techniques, only 14OAc,Z5-14OAc, andZ7-14OAc were found to be behaviorally active. The sex pheromone glands of females of other species including,Planotortrix MBS,Planotortrix M,P. notophaea, Ctenopseustis servana, and aC. obliquana sibling species, were also found to containZ5-14OAc orZ7-14OAc, singly or in combination. In the case ofPlanotortrix M, the addition ofZ7-14OAc to the previously identified sex pheromone blend ofZ5-14OAc and 14OAc was found to increase trap captures of male moths of this species. Thus in these New Zealand species (and in some Australian species),Z5-14OAc andZ7-14OAc appear to be utilized in combination in pheromonal communication just as (Z)-11-tetradecenyl acetate and (E)-11-tetradecenyl acetate are used by many species of Holarctic Tortricidae in the tribe Archipini.Lepidoptera: Tortricidae: Tortricinae.     

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.     

Aggregation pheromone characterization and comparison inDrosophila ananassae andDrosophila bipectinata

(Z)-11-Octadecenyl acetate (Z11–18Ac) and (Z)-11-eicosenyl acetate (Z11–20Ac) were identified as the aggregation pheromones ofDrosophila ananassae, andZ11–20Ac was identified as the aggregation pheromone ofDrosophila bipectinata. Z11–18Ac andZ11–20Ac were not attractive alone; however, in combination with fermenting food odors, the acetates attracted flies of both sexes in a wind-tunnel olfactometer. The pheromones were present in the ejaculatory bulb of sexually mature male flies and transferred to the female during mating. MaleD. bipectinata released little if anyZ11–20Ac to the food; however, recently mated females releasedZ11–20Ac to the surrounding surfaces in just a few hours after mating.D. ananassae males, on the other hand, appeared to release moreZ11–18Ac andZ11–20Ac to the surroundings than mated females. AlthoughD. bipectinata males had noZ11–18Ac, flies were as attracted toZ11–18Ac as to an equal quantity ofZ11–20Ac.D. ananassae were attracted toZ11–18Ac but not toZ11–16Ac orZ11–20Ac. However,Z11–20Ac in combination withZ11–18Ac was significantly more attractive thanZ11–18Ac alone.     

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.     

Geographic Variation in Sex Pheromone of Asian Corn Borer, Ostrinia furnacalis, in Japan

Geographic variation in the sex pheromone of the Asian corn borer, Ostrinia furnacalis (Guenée), was surveyed in populations sampled at four locations ranging from 39.7°N to 32.9°N in Japan. The sex pheromone of the three northern populations was composed of (E)- and (Z)-12-tetradecenyl acetates with a mean E proportion of 36–39%. The southernmost population (Nishigoshi) had the same components but with a significantly higher E composition of 44%. The frequency distribution of the E ratio in the Nishigoshi population exhibited a small peak near 38% and a major peak near 46%. A family-wise analysis of the sex pheromone of this population confirmed that there were two distinct phenotypes regarding the E ratio. An 46% E strain inhabits southern parts of Japan, in addition to an 38% E strain, which seems to be predominant in other regions of Japan.     

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.     

Sex pheromone chemistry of the western spruce budwormChoristoneura occidentalis Free

SCOT capillary Chromatographic and SCOT capillary chromatographic-mass spectrometic analyses of gland washes and effluvia of virgin femaleChoristoneura occidentalis Free, have been conducted with both a diapausing and nondiapausing strain of this insect. The following compounds were identified in gland washes and effluvia in both strains:E andZ11–14Ald,E andZ11–14Ac,E andZ11–14OH and 14Ald, 14Ac, and 14OH. The average aldehyde: acetate: alcohol ratio found by analysis of single glands by virgin females (nondiapausing strain) was 170.73. Analysis of virgin female effluvia gave this ratio as 1038 (diapausing strain: %Z=8, 11, 15, respectively) and 1036 (nondiapausing strain: %Z=8, 11, 12, respectively). The saturated components were generally 1–2% of theE isomer in each case. Comparisons of EAG responses of bothC. occidentalis andC. fumiferana toE11–14Ald,E11–14Ac andE11–14OH were made. Correlations with both laboratory and field data previously published were also made betweenC. fumiferana andC. occidentalis.Lepidoptera: Tortricidae.     

Note of the estimation of the Θ temperature and Ψ parameter from the critical temperature data

Summary Critical values of the polymer volume fraction _2,c and the interaction parameter _c have been computed for the case that the equation for the chemical potential of solvent contains terms _{c 2} ³ and _{c 2} ⁴ in addition to ₂ ² . For 0 _c 1/3, the limits for infinite chain length are _2,c = 0 and _c = 0.5. Quite different results are obtained for _c > 1/3, _2,c being finite and _c lower than 1/2. Conclusions for the estimation of the temperature and the entropy-of-dilution parameter are discussed.     

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.     

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.     

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.     

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.     

Effects of dodecyl acetate andZ-10-tridecenyl acetate on attraction ofEupoecilia ambiguella males to the main sex pheromone component,Z-9-Dodecenyl acetate

Attraction ofE. ambiguella males toZ-9-dodecenyl acetate (Z9-12Ac), alone and in combination with dodecyl acetate (12Ac) orZ-10-tridecenyl acetate (Z10-13Ac) was tested in both wind-tunnel and field experiments. In the laboratory, response toZ9-12Ac reached a distinct dosage optimum at which attraction was nearly as good as to live females. Addition of 12Ac, a minor component of female glands and effluvia, had no effect at low doses ofZ9-12Ac and only marginally improved attraction at the optimum. However, inclusion of 12Ac with an overdose ofZ9-12 Ac fully restored activity. In the field,Z9-12Ac alone was not very attractive at any dose; catches markedly increased by adding 12Ac and climbed with increasing dose of each compound up to 10 mg. Optimum ratio ofZ9-12Ac to 12Ac was 11 to 15. Another compound,Z10-13Ac, had the same effect as 12Ac in the laboratory and the field but was effective at a lower dose. In the field, inclusion of the synergist permits use of high cap loads to attract more males, perhaps from greater distances.     

Chemoattraction between fry of Arctic char [Salvelinus alpinus (L.)] studied in a Y-maze fluviarium

Attraction of fry of Arctic char [Salvelinus alpinus (L.)] to water conditioned by conspecifics of the same age was studied in a Y-maze fluviarium. Two types of experiments were run. In up-swimming tests (1), starting from the common leg of the Y-maze, a single fish was given the choice of entering one of the two upstream arms. In gradient tests (2), the momentary positions of a single char were time-lapse photographed in a test yard of this common shank. Strong attraction to conditioned water was observed in both types of tests.     

Chemistry of Combustion Waves in Substances with a Complicated Structure of Reagent Molecules. 1. Structure of the Front of Rich Isopentane Flame

Results on the structure of the lowtemperature relaxation zone of the front of a laminar Bunsen flame of isoC₅H₁₂ (2methylbutane) under atmospheric pressure are presented. The flame of a premixed mixture isoC₅H₁₂ + O₂ + Ar with a fueltoair equivalence ratio of 1.7 is examined. The mass fluxes, total rates of reactions of matter consumption and expenditure, balance of substances, and profiles of bulk heatrelease rates are calculated on the basis of the experimental concentration and temperature profiles. The results obtained indicate that there is a vast region of lowtemperature conversion of isopentane in the flame front. It is found that only part of the products sampled by the microprobe from different points of the flame front results from transformations in the lowtemperature region, namely, oxygen, isopentane, water, carbon monoxide, propane, methane, and methanol. Ethylene, propylene, hydrogen dioxide, and formaldehyde are present in the lowtemperature zone in insignificant amounts; they are secondary products of conversion of methyl and propyl radicals. It is assumed that the observed feature is a result of the competing interaction of two mechanisms of fuelmixture conversion: selfcatalysis and thermal selfacceleration. Based on the previously suggested mechanism of oxidation pyrolysis by the scheme of intramolecular quadratic destruction, experimentally observed fragmentation of the isopentane molecule is demonstrated. In contrast to npentane, formation of methyl alcohol has been found in isopentane convection products.     

Redundancy in a chemical signal: Behavioral responses of maleTrichoplusia ni to a 6-Component sex pheromone blend

The flight response of maleTrichoplusia ni was observed in a flight tunnel to a sex pheromone blend composed of six components:Z7–12Ac, 12Ac,Z5-12Ac, 11-12Ac,Z7-14Ac, and Z9-14Ac. The number of males reaching a 3000-g source of this blend was > 95%, equal to that observed to female glands and significantly greater than with the previously identified two-component blend (Z7-12Ac + 12Ac). In subtraction tests, all five-component blends, with the exception of the blend lacking the primary componentZ7-12Ac, and several four-component blends elicited similar peak levels of upwind flight, source contacts, and hairpencil displays to that observed with the six-component blend. We characterize the substitution of certain minor components for one another as a form of redundancy in the chemical signal and suggest that it contributes to response specificity and signal recognition in males. The results also support the concept that the full blend of components acts as a unit to influence male behavior at all phases of the response. Individual minor components were not responsible for eliciting specific behaviors in the sequence.     

Dose and enantiospecific responses of white pine cone beetles,Conophthorus coniperda,to alpha-Pinene in an eastern white pine seed orchard

The white pine cone beetle, Conophthorus coniperda, exhibited dose and enantiospecific responses to -pinene in stands of mature eastern white pine, Pinus strobus, in a seed orchard near Murphy, North Carolina, USA. (–)--Pinene significantly increased catches of cone beetles to traps baited with (± )-trans-pityol. (+)--Pinene did not increase catches of beetles to pityol-baited traps and interrupted the response of beetles to traps baited with (±)-trans-pityol and (–)--pinene. Maximal attraction of cone beetles to pityol-baited traps was obtained with lures releasing (–)--pinene at a rate of 103 mg/day at 23^°C. Lures releasing (–)--pinene at rates lower or higher than 103 mg/day resulted in reduced catches to traps baited with (±)-trans-pityol. The sex ratio in all catches was heavily male biased. Attraction of the clerid predator, Thanasimus dubius, to traps baited with (±)-trans-pityol increased significantly with the presence of -pinene, irrespective of enantiomeric composition. Maximal attraction of T. dubius to pityol-baited traps occurred with devices releasing (–)--pinene at the highest rate tested, 579 mg/d at 23^°C, a sub optimal rate for cone beetles.     

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.     

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.     

Chemical composition of degrading mangrove leaf litter and changes produced after consumption by mangrove crabNeosarmatium smithi (Crustacea: Decapoda: Sesarmidae)

The leaves of the mangroveCeriops tagal contained 3.2–4.1% (all percentages relate to dry weight) ofd-1-O-methyl-muco-inositol previously unreported in mangroves. They consisted of 37% aqueous acetone-water-soluble material, 18% water-insoluble polysaccharides, and ca. 50% polyphenols, which include soluble and insoluble tannins and lignin. The polysaccharide component sugars were glucose, arabinose, uronic acids, mannose, xylose, galactose, and rhamnose in the proportions 28262210752, respectively. The leaves were pectate rich, and the low level of glucan was presumed to consist mainly of cellulose. After four weeks of biodegradation, ca. 60% of the acetone-water-soluble material was lost from the leaves. Degradation processes greatly altered the polysaccharide components in the leaves. Pectates were rapidly degraded, while other polysaccharides, although reduced proportionately, resisted degradation at about the same level, and all component sugars were found in the 8-week-old leaves. Apparent lignin contents increased from 15 to >30% during biodegradation up to eight weeks. The yields of the major fractions in corresponding fecal material fromNeosarmatium smithi showed a similar trend to the diets. An enrichment of the insoluble residue was noticeable due to the digestion of dialyzable material. The fecal carbohydrate content was greatly reduced (7–11%) and the apparent lignin increased (27–39%) due to its resistance to degradation. All dietary polysaccharide component sugars were found in the fecal residues, including some uronic acids. The leaves also contained a readily water-soluble fraction (15%) which consisted of pectates strongly complexed with proanthocyanidins.