Pd/silica cluster catalysts: synthesis and reactivity with H2 and C2H4

Silica-supported Pd clusters were characterized by in situ EXAFS spectroscopy. Clusters with an average nuclearity of six atoms were derived from either an inorganic or an organometallic precursor by reduction at 100–150C. Despite the small size of the clusters, EXAFS contributions from the metal-support interface were not detected. These clusters and larger ones formed by reduction at 320C absorb hydrogen on cooling in H₂ to 30C; the resultant interstitial hydride species decompose in vacuo at 30C. Vacuum treatment at 300C removes chemisorbed H₂ yielding bare Pd clusters. In contrast to larger crystallites, the Pd clusters do not react with C₂H₄ at 150 to form interstitial carbide species.     

Attraction ofCacoecimorpha pronubana male moths to synthetic sex pheromone blends in the wind tunnel

Attraction ofCacoecimorpha pronubana male moths to blends of four sex pheromone components was studied in the wind tunnel.Z11–14Ac alone did not elicit upwind flight, admixture of 10%Z11–14OH or more led to successful attraction of males to the source. Attractivity of these binary blends was further enhanced by addition ofE11–14Ac orZ9–14Ac; the optimum was a blend ofZ11–14Ac,Z11–14OH,E11–14Ac, andZ9–14Ac at the proportion of 1003033. In ternary and quaternary blends, the effect ofZ11–14OH andE11–14Ac was strongest at 30% and 3%, respectively. By contrast,Z9–14Ac increased behavioral responses over a wide range.     

Selective vapor phase hydroformylation of ethylene over cluster-derived cobalt catalyst

Vapor phase hydroformylation of ethylene was studied with silica-supported metal catalysts. A cobalt metal catalyst derived from Co₂(CO)₈ gave propanal and its derivatives in as high selectivity of about 36% as Rh/SiO₂ catalyst under the reaction conditions of 1.1 MPa of a gas-mixture of ArCOC₂H₄H₂ = 1333 at 423–503 K. On the other hand, conventional cobalt catalysts derived from cobalt nitrate, chloride, or acetate, and other noble metal catalysts (Pd/SiO₂ and Ir/SiO₂) produced mainly ethane.     

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.     

Field response ofDendroctonus brevicomis toexo-brevicomin,frontalin, and myrcene released at two proportions and three levels

Racemicezo-brevicomin, racemic frontalin, and myrcene were released at two proportions (51400 and 111), each at three levels (1 ×, 10 ×, and 100 ×) in a ponderosa pine forest in central California. The 51400 mix was based on an estimate of the relative amounts released from a ponderosa pine under attack by the western pine beetle,Dendroctonus brevicomis. MoreD. brevicomis were trapped at a source of the three compounds released at 51400 than were trapped at a source released at 111, at all three levels, but this difference was statistically significant only at the 1 × and 10 × levels. Sex ratio of trapped beetles and distribution of catch at the source of attractant and 5 m away apparently did not differ between relative release rates.Coleoptera: Scolytidae.Trade names are mentioned solely for information. No endorsement by the U.S. Department of Agriculture is implied.     

Identification of sex pheromones of two sibling species in dingy cutworm complex,Feltia jaculifera (GN.) (Lepidoptera: Noctuidae)

The sex pheromone components of the two sibling species of the dingy cutworm that occur on the prairies of western Canada were identified in abdomen-tip extracts from calling female moths. Three monounsaturated acetates, (Z)-7-dodecenyl acetate, (Z)-9-tetradecenyl acetate, and (Z)-11-hexadecenyl acetate, are common to both species in ratios of 100133 for species A and 0.30.5100 for species B. The most effective synthetic blends for the attraction of male moths in the field consisted of these three components in ratios of 1010 at 8.8g/lure for species A and 112000 at 500g/lure for species B. The addition of Z5-12Ac to either blend reduced the catches and the addition of Z7-12OH orZ11-16OH to the three-component blend reduced the catches of species B males. The species are morphologically indistinguishable, but the identity of the males attracted to the synthetic blends could be confirmed by their antennal responses to a test blend of the three components using a GC-EAD system. Both synthetic attractant blends are competitive with females and will be useful for studying the distribution, biology, and relative abundances of the two species.Contribution no. 3879005 of the Lethbridge Research Station.     

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.     

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.     

Behavioral responses of maleArgyrotaenia velutinana (Lepidoptera: Tortricidae) to components of its sex pheromone

Males of the redbanded leafroller,Argyrotaenia velutinana (Walker) (Lepidoptera: Tortricidae), were studied for their behavioral responses in laboratory olfactometers and in the field to the 3 components of the female-produced sex pheromone:cis-11-tetradecenyl acetate (c11–14Ac),trans-11-tetradecenyl acetate (t11–14Ac), and dodecyl acetate (12Ac). Dodecyl acetate, when evaporated with c11–14Ac (8%trans) in the field, modified the behavior of feral males nearby the chemical source, causing an increase in the frequency of landing and close approach to the pheromone dispenser. Apparently, an inflight behavioral modification concerning landing or not landing occurs within 60 cm of the source and is mediated by 12Ac. In laboratory olfactometers, c11–14Ac (8%trans) demonstrated a lower threshold for male activation than pure c11- and t11–14Ac and blends of the two isomers. Additionally, over a wide range of dosages, males responded with optimum wing-fanning response to c11–14Ac (8%trans) compared to pure c11–14Ac, c11–14:Ac (30%trans), and pure t11–14Ac, suggesting that thecistrans ratio rather than absolute amounts of either isomer, is a crucial factor in eliciting male response. When presented with c11–14Ac (8%trans) (11), dodecyl acetate caused a significant prolongation of wing-fanning over c11–14Ac (8%trans) alone and resulted in a greater percentage of males moving upwind to the source. Since the increase in wing-fanning and orientation occurred at higher concentrations of the 3-component mixture, the effect of 12Ac in the laboratory may reflect the close-range role of 12Ac in the field.     

Apple ermine moth,Yponomeuta malinellus Zeller Two components of female sex pheromone gland highly effective in field trapping tests

When electroantennographic responses of maleYponomeuta malinellus Zeller to model compounds were determined at dosages of 0.3–30 ng, the strongest responses were obtained from (Z)-9-dodecen-1-ol acetate (Z9–12Ac). Also, strong responses were obtained from (Z)-11-tetradecenal (Z11–14A1) and (Z)-11-tetradecen-1-ol (Zl1–14OH). At a dosage of 0.3 ng,Z11–14A1 produced a stronger response thanZ11–14OH, while at a dosage of 30 ng,Z11–14OH andZ11–14A1 produced equal responses. Gas chromatographic and mass spectral analysis of extracts of female sex pheromone glands showed the presence ofZ9–12Ac, tetradecan-1-ol (14OH), (E)-11-tetradecen-1-ol (E11–14OH),Z11–14OH, hexadecan-1-ol, and hexadecan-1-ol acetate in a ratio of 0.62003710014035. In field tests,Z9–12Ac andZ11–14OH together were required for trap catch, and addition ofZ11–14A1,E11–14OH, 14OH, or (Z)-11-tetradecen-1-ol acetate did not increase catch. Ratios in rubber septa of 0.599.5 to 1.598.5 (Z9–12 Ac/Z11–14OH) captured the most males and captures were statistically equivalent for dosages of 10–1000 g/rubber septum. Traps baited with the synthetic lure produced better catches than those baited with females.Lepidoptera: Yponomeutidae.     

Investigation of sex pheromone components of female asian corn borer,Ostrinia furnacalis (Hübner) (Lepidoptera: Pyralidae) in Taiwan

(E)-12-Tetradecenyl acetate (E12–14OAc), (Z)-12-tetradecenyl acetate (Z12–143nOAc), and tetradecanyl acetate (14OAc) were extracted and identified as major chemical components from female tips of the Asian corn borer,Ostrinia furnacalis (Hübner) (Lepidoptera: Pyralidae) in Taiwan, with a combined wash ratio of 483715 and an individual female ratio of 453916. The average amount ofE12-,Z12–14OAc and 14OAc in each female gland was 6.6±4.6, 5.8±3.5, and 2.4±1.7 ng/female, respectively. The mixture of these three synthetic chemicals not only gave strong activities in male antennae but also could catch significantly more males than virgin females in field-trapping tests. The field test also showed no significant difference in trapping ability among the three-component Taiwan formulations, the two-component Taiwan formulation (Z12–14OAc andZ1214OAc, 5347), and the Japan formulation (Z12–14 OAc andE 12–14OAc, 3:2).     

Zirconium tetra-n-butylate modified with different organic acids: Hydrolysis and polymerization of the products

In this work; (a) complexation reaction of zirconium tetra-n-butylate, Zr(OBu ⁿ )₄, with MAc and different organic acids. (b) the hydrolysis reaction of modified Zr species, and (c) the polymerization reaction of complex products are studied. Zr(OBu ⁿ )₄ was reacted with different mole ratios of methacrylic acid (MAc) at room temperature and the maximum combination ratio was found to be 12 [Zr(OBu ⁿ )₄MAc] by FT IR. The modification of zirconium tetra-n-butylate with the acid mixtures [methacrylic acid-acetic acid (MeCOOH), methacrylic acid-propionic acid (EtCOOH), methacrylic acidbutyric acid (PrCOOH)] was made for a combination ratio of 111 [MAcRCOOHZr(OBu ⁿ )₄RMe. Et, Pr] and the products were characterized by¹H-NMR, FT-IR, and UV-spectroscopies. Following their synthesis, hydrolysis of the complexes with various amounts of water and polymerization with benzoyl peroxide were realized. The hydrolysis and polymerization products of the complexes were studied by Karl-Fischer Coulometric titration and thermal analysis respectively. Methyl-ethyl-ketone (MEK) and chloroform were chosen as solvents.     

Life of silicon carbide heaters in argon at high temperatures

Conclusions The electrical heating elements made from silicon carbide in argon age slowly and may operate for more than 300 h at a temperature on the surface of 1700C and more than 200 h at 1800C.The service life of the heating elements made from silicon carbide at 2000C in argon is less by a factor of 20 than at 1800C. At 2000C sublimation of the SiC from the heating element is observed.The presence in the argon atmosphere of up to 11% oxygen does not have a marked influence on the rate of oxidation of the heating elements at 1600C at the surface.Translated from Ogneupory, No. 3, pp. 33–36, March, 1967.     

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.     

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.     

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.     

Structural studies of Pt-Sn catalysts on high and low surface area alumina supports

For a series of catalysts containing 1 wt. % Pt and SnPt ratios ranging from ca. 1 to 8, the only crystalline alloy phase detected by XRD was SnPt (11). The XRD intensity of lines for the SnPt (11) alloy phase increase with increasing SnPt ratios, indicating the presence of unalloyed Pt in the samples containing low tin loadings.     

Temporal patterns of sex pheromone titers and release rates inHolomelina lamae (Lepidoptera: Arctiidae)

Six hydrocarbon components (2-methylhexadecane,n-heptadecane, 2-methylheptadecane, 2-methyloctadecane,n-nonadecane, and 2-methylnonadecane) were identified in sex-pheromone gland extracts and in airborne collections ofHolomelina lamae. Low variability in the ratio of components among individuals indicates tight regulation of blend composition. Minor changes were evident in the quantity and ratio of the blend as a function of time of day. Based on gland extracts, the total quantity of the six components increased from day 1 (X = 6299 ng) to day 4 (X = 7498 ng) and subsequently decreased. No significant correlations were found between total gland contents and wet or dry weights of moths. Emission rates ofH. lamae females were determined from pheromone adsorbed onto Porapak Q. Quantities released peaked shortly after the onset of calling and decreased rapidly as calling continued. Peak release rates ranged from 13 to 350 ng/10 min, and from 37 to 835 ng/60 min. Noncalling females did not emit detectable quantities of pheromone. Based on release rates and the rate of pulsation of the abdominal tip, the average amount released per pulse is not constant. The mean ratio of components released (0.787.45 84.802.842.591.53) was not very different from the ratio of components in gland extracts of 2-day-old females (0.704.1990.12 1.651.911.42). We propose that the blend is atomized rather than volatilized from the gland, thus retaining nearly the same ratios in the female's effluvium as in her gland.     

Sex pheromone of the armyworm,Pseudaletia unipuncta (Haworth) (Lepidoptera: Noctuidae)

(Z)-11-Hexadecen-1-ol acetate (Z11–16Ac) free of theE isomer (<1%), hexadecan-1-ol acetate (16 Ac), and a hexadecen-1-ol [the (Z)-11 isomer based on the retention time on a Carbowax capillary column] were identified in extracts of the sex pheromone glands of adult virgin female armyworms,Pseudaletia unipuncta. Also, gas Chromatographic retention times on polar and nonpolar columns indicated the possible presence of (Z)-9-hexadecen-1-ol acetate (Z9–16Ac). The ratioZ11–16Ac/16Ac/Z11–16OH/Z9–16Ac was 10.150.130.02. Infield testsZ11–16 Ac was attractive alone, and the addition ofZ9–16Ac,Zll–16 OH, or 16 Ac singly or in combination in ratios found in the gland did not increase trap capture.Mention of a proprietary product does not constitute an endorsement of this product by the USDA.     

Sex pheromone ofGrapholita funebrana occurrence ofZ-8- andZ-10-Tetradecenyl acetate as secondary components

Z-8-Dodecenyl acetate (Z8–12Ac),E-8-dodecenyl acetate (E8–12Ac),Z-8-tetradecenyl acetate (Z8–14Ac),Z-10-tetradecenyl acetate (Z10–14Ac), andZ-8-dodecen-1-ol (Z8–12OH) were identified in the proportions 10013052 in female sex gland extracts ofGrapholita funebrana, accompanied by saturated acetates from 12 to 20 carbons with tetradecyl acetate predominating.Z10–14Ac has not previously been described as a lepidopteran sex pheromone component. Best attraction of males is obtained withZ8–12Ac in the presence of a higher proportion ofE8–12Ac than in the female. Inclusion of the 14-carbon acetates did not augmentG. funebrana catches but inhibitedG. molesta. On the other hand, addition ofZ8–12OH at the level optimal forG. molesta reduced attraction ofG. funebrana.