Biological activity of synthetic hydrocarbon mixtures of cuticular components of the female housefly (Musca domestica L.)

Mixtures of (Z)-9-alkenes (C₂₁-C₃₃),n-alkanes (C₂₁-C₃₃), and mono- and dimethylalkanes (C₂₇, C₂₉), as components of the cuticular lipids washed from the female housefly (Musca domestica L.), were synthesized and assayed for their biological activity on male houseflies. The (Z)-9-alkenes and their hydrogenatedn-alkanes were synthesized from jojoba wax components by the appropriate chain elongation. The methylalkanes were prepared by Grignard coupling reaction of the appropriate alkyl halides, catalyzed by Li₂CuCl₄. Six- to 7-day-old virgin male houseflies exhibited the highest mating strike activity toward 6- to 7-day-old virgin females. The mating strike activity of the synthetic hydrocarbons was studied by exposing 6- to 7-day old virgin males to petrol-ether-rinsed 1 to 2-day-old dead females treated with these chemicals. (Z)-9-Tricosene was the most active hydrocarbon tested when it was applied in amounts of 10 g to a washed dead female. Amounts of 5 g of (Z)-9-tricosene did not cause sexual activity in the males. Mixture of (Z)-9-alkenes showed low activity when applied at 10-g amounts. However, when mixtures were made of 5 g of (Z)-9-tricosene with 5 fig of each of certain mixtures of (Z)-9-alkenes, the striking activity became as high as that of 10 g of (Z)-9-tricosene. This might be a synergism effect. The mixtures ofn-alkanes, as well as the mono- and dimethylalkanes, showed moderate activity. When (Z)-9-tricosene was added to these materials no increase in male activity was observed.     

(3Z,6Z,9Z)-Nonadecatriene and enantiomers of (3Z,9Z)-cis-6,7-Epoxy-nonadecadiene as sex attractants for two geometrid and one noctuid moth species

Sex attractants for the geometrid mothsEufidonia convergaria andCaripeta angustiorata, and the noctuid mothRivula propinqualis have been elucidated during field screening of a series of (3Z,6Z,9Z)-triene hydrocarbons (C_17–22), and the racemic and enantiomerically enriched monoepoxydienes derived from those hydrocarbons. Biologically active compounds were identified by a combination of field testing of synthetic standards, electroantennography, and coupled gas chromatography-electroantennogram detection.E. convergaria males were optimally attracted by a 11 blend of (3Z,9Z)-(6S,7R)-epoxy-nonadecadiene (3Z,9Z-6S,7R-epoxy-19H); other abbreviations follow the same system) with (3Z,6Z,9Z)-nonadecatriene (3Z,6Z,9Z-19H). The 6R,7S enantiomer of the epoxide had no apparent biological activity, either as an attractant or as a behavioral antagonist. Male moths also were attracted to blends of the C₁₈ and C₂₀ homologs of the triene and the epoxide. 3Z,6Z,9Z-19H and 3Z,6Z-cis-6,7-epoxy-19H were identified inE. convergaria female pheromone gland extracts. Males of the geometrid moth speciesC. angustiorata were attracted by a 11 blend of 3Z,6Z,9Z-19H and enantiomerically enriched 3Z,9Z-6R,7S-epoxy-19H. Males of the noctuid mothR. propinqualis were attracted by an approximately 101 blend of 3Z,6Z,9Z-19H and enantiomerically enriched 3Z,9Z-6S, 7R-epoxy-19H. The components were synergistic, with neither being attractive alone. The blend ratio was quite specific, as the attractiveness of blends decreased sharply on either side of the optimum ratio.Issued as NRC No. 30266.     

Crystal structure and size distribution of Pt-Cu-Fe alloy clusters supported on carbon black

Carbon supported alloy electrocatalysts based on Pt, Cu and Fe (atomic ratios PtCuFe=211 and 611) are prepared at various alloying temperatures and are characterized by XRD and TEM techniques. Powder XRD analyses show that Pt₆CuFe clusters form a face-centered cubic structure (AuCu₃ type), while Pt₂CuFe clusters form an ordered alloy with a facecentered tetragonal structure (AuCu type) at higher temperature than 700C. Transmission electron micrographs reveal that the size of metal clusters increases gradually and size distribution becomes broader, as alloying temperature increases from 500 to 1100C.     

Volatile organic chemicals of a shore-dwelling cyanobacterial mat community

The main components of a cyanobacterial mat community of a hypersaline lake shore consist of edaphic, mat-forming strains (ecophenes), and littoral strains ofOscillatoria animalis Agardh andO. subbrevis Schmidle, other microorganisms associated with these cyanobacteria, several species ofBembidion (Carabidae: Coleoptera), and two halophytic flowering plants:Puccinellia nuttalliana (salt meadow grass) andSalicornia europaea rubra (samphire). The volatile organic compounds of this community are a blend of those emitted by each of these components such as the C₁₇ alka(e)nes, geosmin, 2-methylisoborneol,-cyclocitral,-ionone, dimethyl sulfide, and dimethyl trisulfide of cyanobacteria and associated microorganisms; alcohols, esters, and aldehydes usually associated with flowering plants; and possibly some insect-derived esters, particularly isopropyl tetradecanoate. The dominant compounds were: C₁₁, C₁₃, C₁₅, and C₁₇ alka(e)nes, methyl esters of C₁₆ and C_18:2 acids, isopropyl tetradecanoate, heptanal, 3-octanone and 2-nonanone, the acyclic terpene linalool, and the alcohols 1-heptanol, 1-hexanol, 1-octanol, 3-hexen-1-ol, and 2-octen-1-ol. It is concluded that this community may be distinguished from related communities by its repertoire of volatile organic compounds.     

Olefin as an Intermediate in n-Butane Isomerization on Sulfated Zirconia. An In Situ 13C MAS NMR Study of n-Octene-1 Conversion

By using in situ ¹³C MAS NMR and ex situ GC-MS, the analysis of hydrocarbon products formed from n-octene-1 adsorbed on sulfated zirconia catalyst (SZ) has been performed. It is shown that a mixture of alkanes and stable alkyl substituted cyclopentenyl cations (CPC) is formed as the basic reaction products. Formation of both alkanes and CPC from n-octene-1, a precursor of C₈ ⁺ cation, the key intermediate in n-butane isomerization via a bimolecular pathway, implies that formation of the isomerized alkane occurs by a complex process of conjunct polymerization, rather than isomerization itself. CPC deposited on the SZ surface can be in charge of the catalyst deactivation.     

In situ observation of methoxide hydrogenation on the Ni(111) surface

The surface chemistry of methoxide (CH₃O-) on the Ni(111) surface has been studied in the presence of hydrogen pressures up to 2 Torr. During heating in vacuum methoxide decomposes to H₂ and CO, which desorb at 380 and 445 K, respectively. The CH₃O-decomposition process is rate limited by CH bond breaking and exhibits a strong deuterium kinetic isotope effect in CD₃O-. In the presence of ambient hydrogen pressures of 0.02–2.0 Torr both CH₃O- and CD₃O-are hydrogenated directly to methanol at 310 K. Methoxide is hydrogenated by adsorbed hydrogen, which nearly saturates the surface at these pressures and temperatures.     

An attempt to bridge the pressure and material gap with a disperse model catalyst for low-temperature alkane reforming

Pt black was exposed to n>-hexane/H₂ mixtures between 483 and 663 K followed by O₂ and H₂ treatments at 603 K. XP and UP spectra were measured without exposing the samples to air. 20–30% carbon accumulated after hydrocarbon exposures. O₂ removed most carbon. The surface C content increased after a subsequent contact with H₂, C 1s showing more atomic carbon as opposed to graphite after n-hexane exposure. Anisotropic recrystallization of Pt black favoring (220) and (311) lattice planes occurred under hydrogen-rich conditions. Both findings were attributed to a H₂-induced solid-state rearrangement; H atoms penetrating into the crystal lattice, force subsurface carbon and oxygen atoms to the surface and a concomitant restructuring would occur. Thus another hydrogen effect has been recognized, leading to structures favorable for skeletal reactions of alkanes.     

Mammalian exocrine secretions XV. Constituents of secretion of ventral gland of male dwarf hamster, Phodopus sungorus sungorus

In a study aimed at the chemical characterization of constituents of the ventral gland secretion of the male dwarf hamster, Phodopus sungorus sungorus, 48 compounds, including saturated alcohols, saturated and unsaturated ketones, saturated and unsaturated straight-chain carboxylic acids, iso- and anteisocarboxylic acids, 3-phenylpropanoic acid, hydroxyesters, 2-piperidone, and some steroids were identified in the secretion. The position of the double bonds in -icosadienyl--butyrolactone and -henicosadienyl--butyrolactone, and the position of methylbranching in seven C₁₆–C₂₁saturated ketones could not be established. Several constituents with typically steroidal mass spectra also remained unidentified. The female dwarf hamster's ventral gland either does not produce secretion or produced so little secretion that it was impossible to collect enough material for analysis.     

Learning of Herbivore-Induced and Nonspecific Plant Volatiles by a Parasitoid,Cotesia kariyai

Learning of host-induced plant volatiles by Cotesia kariyai females was examined with synthetic chemicals in a wind tunnel. Wasps were preconditioned by exposure to volatiles and feces simultaneously. A blend of four chemicals, geranyl acetate, -caryophyllene, (E)--farnesene, and indole, which are known to be specifically released from plants infested by host larvae Mythimna separata (host-induced blend), elicited a response in naive C. kariyai, but did not enhance the response after conditioning. A blend of five chemicals, (E)-2-hexenal, (Z)-3-hexen-1-ol, (Z)-3-hexen-1-yl acetate, -myrcene, and linalool, which are known to be released not only from plants infested by the host larvae, but also from artificially damaged plants or undamaged ones (unspecific blend), elicited little response in naive wasps, but significantly enhanced the wasps' response after conditioning. With a blend of the above nine chemicals, wasps could learn the blend at lower concentrations than they did in the nonspecific blend. Hence, both the host-induced and nonspecific volatile compounds appear to be important for C. kariyai females to learn the chemical cues in host location.     

Synthesis and Redox Properties of a π-Conjugated Cyclobutadienecobalt Polymer Containing Ferrocenyl Groups

The reaction of CpCo(PPh₃)₂, in which Cp= ⁵-cyclopentadienyl, with a -conjugated diacetylene, FcCC–o-C₆H₄–CCFc, in which Fc=ferrocenyl, was found to give a cyclobutadienecobalt mononuclear complex, { ⁴-C₄Fc₂(o-FcC₆H₄)₂}CoCp (1), the crystal structure of which was determined by X-ray crystallography. In contrast, the reaction of CpCo(PPh₃)₂ with FcCC–p-C₆H₄–CCFc affords a cyclobutadienecobalt polymer, [p-C₆H₄( ⁴-C₄Fc₂)CoCp] _n (2). The monocobalt complex 1 shows reversible 1e^– and 3e^– redox waves at E ⁰=0.116 and 0.350 V vs Ag/Ag⁺, and the polymer complex 2 shows two chemically reversible redox waves at E ⁰=0.143 and 0.219 V for the oxidation of the ferrocenyl moieties in the cyclic voltammogram. Crystal data are as follows: (1, C₆₅H₄₉CoFe₄), triclinic, space group P\={1} (No. 2), a=13.547(4), b=16.197(4), c=11.763(4) Å, =106.79(2), =97.93(3), =97.12(3), V=2410(1) ų, Z=2.     

Genetic aspects of interpopulational differences in pheromone blend of cabbage looper moth,Trichoplusia ni

The genetic basis of interpopulational differences in the pheromone blend emitted by the cabbage looper moth,Trichoplusia ni (Hübner), was examined by crossing individuals from a field-derived population (P₁) with individuals from a long-maintained laboratory colony (P₂). These colonies differed in the emission rate and relative proportions of four of the five known minor pheromone components, but not in the emission rate of the major component, (Z)-7-dodecenyl acetate (Z7-12Ac). These differences in pheromone blend were quantitatively small but biologically significant, because in the field, males responded preferentially to traps baited with a pheromone blend that is similar to that emitted by P₁ females relative to a blend similar to that emitted by P₂ females. In initial crosses, variation in the quantity and quality of pheromone blends among families of P₁, P₂, and F₁ hybrid females was examined. In F₁ females the relative proportions (quantity relative to the major component) of (Z)-5-dodecenyl acetate (Z5-12Ac) and (Z)-7-tetradecenyl acetate (Z7-14Ac) were intermediate to parental lines. In a second more extensive set of crosses, analyses included P₁, P₂, F₁, F₂, and selected backcrosses. The relative proportion of Z5-12Ac, Z7-14Ac, and Z9-14Ac emitted by F₁ females were intermediate to parental lines. The frequency distributions of relative proportions of these components emitted by females were not consistent with those expected under a single autosomal or sex-linked gene hypothesis, suggesting that more than one gene is involved in the quantitative differences in the pheromone blend.     

Neonate Plutella xylostella Responses to Surface Wax Components of a Resistant Cabbage (Brassica oleracea)

Behavior of neonate Plutella xylostella was observed and quantified during the first 5 min of contact with cabbage surface waxes and surface wax components deposited as a film (60 g/cm²) on glass. The time larvae spent biting was greater and the time walking was less on waxes extracted from the susceptible cabbage variety, Round-Up, than on an insect-resistant glossy-wax breeding line, NY 9472. The waxes of both cabbage types were characterized and some of the compounds present at higher concentrations in the glossy waxes were tested for their deterrent effects on larvae by adding them to the susceptible waxes. Adding a mixture of four n-alkane-1-ols or a mixture of - and -amyrins to wax from susceptible cabbage reduced the number of insects biting and, among those biting, reduced the time biting and increased the time walking in a dose-dependent manner. Among individual n-alkane-1-ols, adding C₂₄ or C₂₅ alcohols reduced the number of insects biting but only adding C₂₅ alcohol reduced the time spent biting among those insects that initiated biting. Adding a mixture of five n-alkanoic acids did not affect biting, but increased the time spent palpating and decreased walking time. Among individual n-alkanoic acids, only adding C₁₄ significantly increased the time palpating. If the observed responses were gustatory, the results indicate that some primary wax components, including specific long-chain alkyl components, have allelochemical activity influencing host acceptance behavior by a lepidopteran larva.     

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.     

Attraction ofOryzaephilus surinamensis (L.) andOryzaephilus mercator (Fauvel) (Coleoptera: Cucujidae) to some common volatiles of food

Responses by adultOryzaephilus surinamensis (L.) andOryzaephilus mercator (Fauvel) to various food volatiles were assessed by means of a two-choice, pitfall olfactometer. The individual experimental stimuli, all potential products of lipid oxidation, had a range of attractive doses of 1000-fold over the test dose ranges of 0.001–100 gmg, or 0.01–1000 gmg. Of 13 aliphatic C₃-C₁₄ aldehydes and benzaldehyde tested forOryzaephilus spp., 10 C₃-C₁₀ aliphatic aldehydes and benzaldehyde showed some attractiveness for both species. ForO. mercator, nonanal had the lowest lower threshold for positive response at 0.01 g. The addition of small amounts of nonanal or of a 111 mixture of hexanal, octanal, and nonanal to small amounts of cucujolide aggregation pheromones enhanced response by mixed-sexO. mercator to the pheromones. Eleven aliphatic C₂-C₉ free fatty acids showed some attractiveness for bothOryzaephilus spp. Isovaleric acid and valeric acid had the lowest lower thresholds for positive response at 0.1 g forO. mercator andO. surinamensis, respectively. Four olefinic oat volatiles were found to possess various degrees of attractiveness for bothOryzaephilus spp. The data suggest that food volatiles in this study might be used byOryzaephilus spp. as host-finding kairomones in nature.Research supported by the Natural Sciences and Engineering Research Council of Canada, Strategic Grant G0958 and Operating Grants A3881 and A3785.     

Oxidative coupling of methane at 600 °C on CaNiK oxide catalysts

We are herewith reporting new data which modifies, explains and extends our earlier work on this subject. Previous observations of low CH₄ conversion and high selectivity to C₂ hydrocarbons were erroneous due to the formation of bulk CaCO₃ in the catalyst. The carbonate was detected by powder X-ray diffraction and was shown to accumulate during the reaction and decompose during regeneration. Catalytic runs which incorporated an internal standard revealed a deficit in the C balance consistent with carbonate formation. Actual CH₄ conversions were 20% with 15% selectivity to hydrocarbons. The effect of steam in promoting coupling over combustion was affirmed.     

Defensive secretions of three oxytelinae rove beetles (Coleoptera: Staphylinidae)

The secretions of the abdominal glands ofBledius spectabilis Kraatz,Platystethus arenarius Fourcr., andOxytelus piceus L. have been shown to contain four 1-alkenes; toluquinone; toluhydroquinone; C₁₀ ^–-,C₁₁ ^–, C₁₂ ^–-, and C₁₄ ^– -lactones; C₁₂--lactone; citral; and decyl-, undecyl-, and dodecyl acetates. Quantitative results indicate that 1-alkenes are formed probably from present lactones by decarboxylation. According to the known life histories of the beetles, it is suggested that the gland material is not used as an algal growth regulator but represents a unique defensive blend characteristic for the whole subfamily.     

The effect of support structure on CO2 hydrogenation over a rhodium catalyst supported on niobium oxide

The hydrogenation of CO₂ was investigated over a rhodium catalyst supported on niobium oxide at atmospheric pressure. Niobium oxide was prepared by the hydrolysis of niobium chloride and its crystallitic structure was controlled by calcination temperature. It was found that the activity was lower but the selectivity of C₂₊ hydrocarbons was higher for the and forms than for the and forms of the niobium oxide.     

Fate of quinolizidine alkaloids through three trophic levels:Laburnum anagyroides (Leguminosae) and associated organisms

The quinolizidine alkaloids (QA) of golden rain,Laburnum anagyroides, and those of phytophagous insects associated with the plant, as well as of parasitoids of the latter, were analyzed by capillary GLC and GLC-MS. The alkaloid content in samples of vegetative plant parts was high at the beginning of the season, then decreased, while that of reproductive organs was high throughout flowering, pod formation, and maturation. The analyses showed that the QA of the plant passed through two higher trophic levels (herbivorous insects and their parasitoids) and that the alkaloid pattern changed little during the passage. The alkaloids were present in two phytophagous insect species associated with golden rain: the predispersal seed predator,Bruchidius villosus [5–13g/g fresh weight (fw)], andAphis cytisorum (182–1012g/g fw), an aphid that feeds on shoots, leaves, and inflorescences. Braconid and chalcidoid parasitoids emerging from the bruchid host also contained alkaloids (1.3–3g/g fw), as did three foraging ant species,Lasius niger, Formica rufibarbis, andF. cunicularia (45g/g fw), that visited the aphid colonies or honeydew-covered leaves of aphid-infested plants. The hypothesis that developing bruchid larvae and/or the plant manipulate QA supply to infested seeds was not supported, because QA content of leftover endosperm in seeds after bruchid development was similar to that of uninfested seeds. The frass of developing bruchid larvae was rich in QA (31g/ g dry weight). While aphids sequestered, the bruchid larvae took up and eliminated QA with the frass without chemical transformation.     

Carbon oxides hydrogenation on RhNa-Y: Addition of 1-butene

At 4.0 MPa, CO₂ hydrogenation over a RhNA-Y catalyst yields only saturated and essentially linear hydrocarbons (up to C₇). In contrast, CO hydrogenation gives a more complex mixture including olefins ( and ), paraffins (linear and branched) and oxygenates. Addition of 1-butene provides a plausible interpretation of these differences.     

Effect of Volatile Constituents from <Emphasis Type="Italic">Securidaca</Emphasis><Emphasis Type="Italic">Longepedunculata</Emphasis> on Insect pests Of Stored Grain

Securidaca longepedunculata Fers (Polygalaceae) is commonly used as a traditional medicine in many parts of Africa as well as against a number of invertebrate pests, including insects infesting stored grain. The present study showed that S. longepedunculata root powder, its methanol extract, and the main volatile component, methyl salicylate, exhibit repellent and toxic properties to Sitophilus zeamais adults. Adult S. zeamais that were given a choice between untreated maize and maize treated with root powder, extract, or synthetic methyl salicylate in a four-way choice olfactometer significantly preferred the control maize. Methyl salicylate vapor also had a dose-dependant fumigant effect against S. zeamais, Rhyzopertha dominica, and Prostephanus truncates, with a LD₁₀₀ achieved with a 60 l dose in a 1-l container against all three insect species after 24 hr of exposure. Probit analyses estimated LD₅₀ values between 34 and 36 l (95% CI) for all insect species. Furthermore, prolonged exposure for 6 days showed that lower amounts (30 l) of methyl salicylate vapor were able to induce 100% adult mortality of the three insect species. The implications are discussed in the context of improving stored product pest control by small-scale subsistence farmers in Africa.