Male-specific sesquiterpenes from Phyllotreta and Aphthona flea beetles.

It was previously reported that males of the crucifer flea beetle, Phyllotreta cruciferae, feeding on host foliage are attractive to both males and females in the field. Based on this evidence for an aggregation pheromone, volatiles were collected from male and female P. cruciferae feeding on cabbage (Brassica oleracea) and analyzed. For comparison, volatiles were also collected from males and females of three other flea beetle species, Aphthona flava, A. czwalinae, and A. cyparissiae, all feeding on their host, leafy spurge foliage (Euphorbia esula). Six male-specific compounds were isolated from P. cruciferae, and the same compounds plus two additional ones were isolated from males of Aphthona flava, A. czwalinae, and A. cyparissiae. The blends of compounds were relatively consistent within species, but there were characteristic differences between species. Compound structures were studied by mass spectrometry, NMR spectroscopy, UV spectroscopy, polarimetry, chiral and achiral gas chromatography, molecular modeling, and microchemical tests. Three of the compounds were identified as (+)-ar-himachalene; (+)-trans-alpha-himachalene; (+)-y-cadinene. Two others were new enantiomers of himachalene hydrocarbons that were previously identified from the fir trees, Abies alba and Abies nordmanniana. Finally, there were two himachalene alcohols and one norsesquiterpene ketone that is a himachalene analog. Only (+)-ar-himachalene and (+)-y-cadinene are previously known natural products. Electrophysiological activity was demonstrated for five of the compounds. The chemical and electrophysiological patterns are consistent with, but do not prove, a pheromonal function.

Nonequilbrium quantitation of volatiles in air streams by solid-phase microextraction.

Solid-phase microextraction (SPME) is a valuable technique for analyzing air-borne organic compounds; one important application is measuring concentrations when these are constant over time. Quantitation normally relies on the SPME fiber being fully equilibrated with the sample medium. Unfortunately, relatively heavy compounds do not equilibrate within a reasonable amount of time, and this has limited the scope of SPME. The ability to quantitate during equilibration was needed and was the focus of this investigation. This entailed having an accurate description of SPME kinetics, and the kinetics of extraction by poly(dimethylsiloxane) fibers was studied for alkanes of 9-22 carbons, primary alcohols of 6-13 carbons, and methyl esters of 6-16-carbon acids. Sampling was from air streams in which analyte concentrations were effectively constant, and sampling times ranged from 30 min to 3 days. Other experimental variables included sampling temperature, fiber coating thickness, air flow rate, and tubing diameter in which the SPME sampling took place. Over 1900 data points were acquired. Previous theoretical kinetic models were not applicable to the present experimental conditions, but a simple kinetic equation was formulated that described the data very well; its key property is an explicit relationship between fiber sensitivity and equilibration time. Using nonlinear regression, the equation parameters were linked to known properties of the analyte (the functional group and GC retention index on a nonpolar column) and to certain sampling conditions (temperature, sampling duration, air flow rate, tubing diameter). The regression equation serves as a practical quantitation formula and allows the absolute concentration of the analyte in the air stream to be calculated directly from the amount extracted by the SPME fiber (which is easily measured by GC), regardless of whether equilibrium has been established or not, as long as the above analyte properties and sampling conditions are known. The residual variability for the model (RSD = 9.4%) was only slightly larger than the variability inherent in SPME alone (∼5%). Considerations for SPME sampling from air are discussed, and new fiber calibration information is presented for the larger hydrocarbons, alcohols, and methyl esters.

Dithyreanitrile: an unusual insect antifeedant from Dithyrea wislizenii.

Dithyreanitrile, a novel sulfur-containing indole alkaloid, was isolated from the seeds of Dithyrea wislizenii (Cruciferae). Dithyreanitrile inhibits feeding of fall armyworm (Spodoptera frugiperda) and European corn borer (Ostrinia nubilalis) larvae. Dithyreanitrile, the first natural product with two sulfur atoms and a nitrile attached to the same carbon, was characterized by X-ray diffraction, spectroscopy, and chemical synthesis.

Limonoid antifeedants from seed of Sandoricum koetjape.

An extract of the seed of Sandoricum koetjape has yielded two new limonoids, sandoricin [1] and 6-hydroxysandoricin [2]. Both compounds are effective antifeedants when incorporated into artificial diets and fed to fall armyworm (Spodoptera frugiperda) or European corn borer (Ostrina nubilalis) larvae. Reduced growth rates and increased times to pupation were evident at lower dose levels while significant mortality was noted at higher dose levels. Structures of both compounds were determined by 1H nmr, 13C nmr, and ms and confirmed by X-ray crystallography.

Effect of meliaceous seed extracts on growth and survival ofSpodoptera frugiperda (J.E. Smith).

Hexane and ethanol extracts of seeds from 10 plant species (including neem-Azadirachta indica A. Juss.) of the family Meliaceae were incorporated into artificial diet at various doses and fed to fall armyworm [Spodoptera frugiperda (J. E. Smith) (Lepidoptera: Noctuidae)] larvae in nochoice tests. All produced significant mortality, reduced larval growth rate, increased time to pupation, or all three, at some concentration. The two highest doses of all of the ethanol extracts caused 100% mortality before pupation, but the hexane extracts tended to be less effective.Aglaia cordata Hiern. ethanol extract was as potent as the comparable neem seed extract at virtually all levels, and its hexane extract was active at much lower concentrations than the neem extract was. The sublethal effects (slower growth and increased time to pupation) were usually detectable at lower doses of extract than mortality was.

Structure-activity relationships among maytansinoids in their effect on the European corn borer,Ostrinia nubilalis (Hübner).

Five maytansinoids fromMaytenus (Celastraceae) andPutterlickia (Rhamnaceae) species were tested for biological activity against the European corn borerOstrinia nubilalis. Maytanbutine, maytansine, and maytanvaline, all of which contain an amino acid residue at C-3, were active and comparable in their effect on larvae to trewiasine, a known active, amino acid-containing maytansinoid fromTrewia nudiflora. Maytanacine, which has an acetate group at C-3, was not as active as maytansine, maytanvaline, maytanbutine, or trewiasine, but significantly retarded the development of the larvae. Normaysine, which has no oxygen substituent at C-3, had no significant effect on mortality and only moderate effect on development of the larvae. The presence of the amino acid moiety at C-3 appears to be an important factor for the biological activity of maytansinoids.

Volatile food attractants forOryzaephilus surinamensis (L.) from oats.

The sawtoothed grain beetle,Oryzaephilus surinamensis (L.) (Coleoptera: Cucujidae), is attracted to certain volatile components that occur in whole and rolled oats as determined by a laboratory pitfall chamber bioassay. More than 100 components were detected in the attractive carbonyl-containing fractions; 14 of these, making up 60% of the total, were identified and bioassayed. Although hexanal, heptanal, octanal, (E)-2-heptenal, and 2-furaldehyde, at doses ranging variously from 1 to 100 µg, were all significantly attractive, only 1 /10 to 1 /100 as much (E)-2-nonenal or (E,E)-2,4-nonadienal was necessary to produce comparable insect response. In addition, propanal and formaldehyde (previously reported in oats but not detected by us) were bioassayed and found to be attractive.