Development of a bioluminescence assay for aldehyde pheromones of insects

A newly developed bioluminescent assay was used to measure quantitatively the amount of (E)-11-tetradecenal, the major component of the sex pheromone of the spruce budworm, trapped on Porapak Q^®. The bioluminescent response was linearly related to the amount of aldehyde either deposited on the absorbent or trapped from an airstream. However, the recovery of pheromone from Porapak was dependent on whether the air was prefiltered (through Porapak) or taken directly from the atmosphere. Furthermore, pheromone on Porapak was lost with time during the flow of air through the absorbent, indicating that trapping of aldehyde pheromone should be conducted for short periods of time for optimal recoveries. The applicability of the assay system for the rapid and direct measurement of the release rates of aldehyde pheromone lures was demonstrated for pheromone lures used for baiting spruce budworm traps.This investigation was supported by the U.S.D.A. Forest Service Program entitled Canada United States Spruce Budworms Program (23–345) and the Medical Research Council of Canada (MT-4314).     

Collection on Porapak Q of the aggregation pheromone ofScolytus multistriatus (Coleoptera: Scolytidae)

The attractive volatiles in the air around the virgin female of the smaller European elm bark beetle,Scolytus multistriatus (Marsham), tunneling in elm logs can be collected by passing the air through a column of Porapak Q. These volatiles can be removed from the Porapak by Soxhlet extraction with hexane, yielding an extract that is attractive to in-flight beetles in the field. GLC analyses of this extract and an extract of virgin female frass indicate that the aeration extract contains active chemicals that are not in the extract of frass.     

Host selection byHylemya antiqua laboratory bioassay and methods of obtaining host volatiles

An oviposition bioassay for the onion maggot,Hylemya antiqua (Meigen), is described in which females, in response to volatile stimulants, oviposit through small apertures onto moistened filter paper. Onion volatiles that act as attractants and oviposition stimulants were captured in Porapak Q from air passed over chopped onions in glass chambers. Pentane extracts from odor-impregnated Porapak Q induced 30–50% of the oviposition that occurred in response to 15-g onion-slice stimuli. Extracts presented in pentane on waxed dental cotton wicks induced more constant oviposition over a 3-day period than extracts on unwaxed wicks. Extract of the Porapak Q-captured volatiles from bulbs of fresh, actively growing onions elicited a much stronger response than did stem and leaf extracts from the same onions. The bioassay techniques and chemical procedures developed in this study could be used in chemical isolation programs for host attractants or oviposition stimulants forH. antiqua or similar species.Diptera:Anthomyiidae.Research supported by National Research Council of Canada, Grant Nos. A3881 and A3706.     

6,6'-二甲基-2,2'-联吡啶固相萃取光度法测定水中铜的研究

根据试剂6,6' 二甲基 2,2' 联吡啶与铜(Ⅰ)的显色反应及WatersPorapakR○　Sep Park固相萃取小柱对显色配合物的固相萃取,建立了一种测定水样中μg/L级铜的新方法,在pH=4.5HAc NaAc缓冲介质中,6,6' 二甲基 2,2' 联吡啶与铜(Ⅰ)反应生成2∶1稳定配合物,该配合物可用WatersPorapakR○　Sep Park固相萃取小柱富集,小柱上富集的配合物用乙醇(内含1%醋酸)洗脱后用光度法测定,可测定水样中μg/L级的铜。该方法用于几种水样中铜含量的测定,结果令人满意。     

Porapak Q色谱柱在大型乙烯联合生产装置分析中的应用

介绍了气相色谱法Porapak Q填充色谱柱在大型乙烯联合生产装置分析中的应用.Porapak Q分别作为预柱及分析柱,主要是在乙烯、丙烯产品中微量CO、CO2,C3以下不凝气,乙烯、丙烯产品中微量氢气,环氧乙烷/乙二醇循环气,槽车中氧含量,丙酮产品中杂质及环氧乙烷中CO2分析中的广泛应用.     

Primary Attraction of the Fir Engraver, Scolytus ventralis

In laboratory bioassays, Porapak Q-captured and steam-distilled volatiles from the bark of host trees, Abies grandis, particularly from root-rot-infected trees, attracted 50–70% of male and female fir engravers, Scolytus ventralis. Gas chromatographic–electroantennographic detection (GC-EAD) analyses of Porapak Q-captured bark volatiles revealed 19 EAD-active compounds of which 13 (mostly monoterpenes) were identified by GC–mass spectrometry (GC-MS). In separate field experiments, multiple-funnel traps baited with two blends of these 13 synthetic volatiles released at 280 and 340 mg/ 24 hr attracted 66 and 93% of the total S. ventralis captured, respectively. The clerid predator, Thanasimus undulatus, also responded strongly to the kairomonal volatiles. Additional experiments produced no evidence for aggregation pheromones in S. ventralis. These included laboratory bioassays and GC and GC-EAD analyses of Porapak Q-captured volatiles from male- and female-infested logs or trees undergoing mass attack in the field, GC analyses and/or bioassays of extracts from female accessory glands, extracted volatiles from emerged, attacking and juvenile hormone-treated beetles of both sexes, and videotape analysis of the behavior of attacking beetles on the bark surface. We argue against the hypothesis of pheromone-mediated secondary attraction in S. ventralis and conclude that the attack dynamics of this species can be explained solely by its sensitive primary attraction response to host volatiles.     

气相色谱法快速测定高纯度二氧化硫气体中水分含量

采用气相色谱法,运用Porapak Q固定相,在柱温100℃时可测定产品SO2气体中水分含量。此方法分离效能高,稳定性好,结果准确。     

Sex pheromone components and calling behavior of the female dermestid beetle,Trogoderma variabile Ballion (Coleoptera: Dermestidae)

Females of the dermestid beetle,Trogoderma variabile Ballion, exhibit a diel pattern of calling behavior. A potent sexual excitant and attractant for the male beetles can be collected on Porapak Q during aeration of female beetles, but cannot be detected in extracts of macerated females. The attractant has been identified as (Z)-14-methyl-8-hexadecenal. Of the five additional compounds previously identified as attractants in otherTrogoderma species, only two were found; (Z)-14-methyl-8-hexadecen-1-ol is present in extracts of macerated female beetles, but not in extracts of Porapak Q, and -caprolactone is present in extracts of Porapak Q. Three collection procedures were necessary to ensure that all the pheromone components had been isolated. Synthetic (Z)-14-methyl-8-hexadecenal elicits attraction and sexual arousal inT. Variabile males.Mention of a commercial or proprietary product in this paper does not constitute an endorsement of that product by the USDA.     

Chemical attractants for the smaller european elm bark beetleScolytus multistriatus (Coleoptera: Scolytidae)

The secondary attractant for the smaller European elm bark beetleScolytus multistriatus is a mixture of three compounds: (-)4-methyl-3-heptanol(I); 2,4-dimethyl-5-ethyl-6,8-dioxabicyclo(3.2.1) octane (II); and (–)-cubebene (III). The novel structure assigned to compound II was confirmed by synthesis. All three compounds were isolated from the volatile compounds collected on Porapak Q by aerating elm bolts infested with virgin female beetles. The GLC fractionations were monitored by two laboratory bioassays. Individually, each compound was inactive in the laboratory bioassays, but a mixture of all three showed activity nearly equivalent to that of the of the original Porapak extract. A mixture of synthetic I and II plus natural III (from cubeb oil) was highly attractive to beetles in preliminary field tests.Supported in part by a cooperative research grant to the State University of New York College of Environmental Science and Forestry, State University of New York, Syracuse, New York, from the USDA Forest Service, Northeastern Forest Experiment Station, Upper Darby, Pennsylvania, and from the Elm Research Institute, Harrisville, New Hampshire.     

Identification of the Major Sex Pheromone Component of the Click Beetle Agriotes ferrugineipennis

Synthetic sex pheromone lures are useful tools to monitor and control populations of adult click beetles (Coleoptera: Elateridae). However, sex pheromones for Agriotes click beetle species native to North America have yet to be identified. Here we report the identification and field testing of the sex pheromone of Agriotes ferrugineipennis. Headspace volatiles from female beetles were collected on Porapak Q, and aliquots of Porapak extract were analyzed by gas chromatographic-electroantennographic detection (GC-EAD) and GC-mass spectrometry. 7-Methyloctyl 7-methyloctanoate (7Me7Me) emitted by females was more abundant and elicited much stronger responses from male antennae than the aldehydes octanal and nonanal and the ketone 6,10,14-trimethyl-2-pentadecanone. In a field experiment, captures of A. ferrugineipennis males in traps baited with candidate pheromone components exceeded those of unbaited control traps, on average by nearly 1,200 times. Neither the ketone nor the aldehydes as lure constituents appeared to alter captures of males in 7Me7Me-baited traps. We conclude that 7Me7Me is the major, and possibly the only, sex attractant pheromone component of female A. ferrugineipennis.

     

Collection of pheromone from atmosphere surrounding boll weevils,Anthonomus grandis

An effluvial method was developed to collect the pheromone, grandlure from actively calling male boll weevils,Anthonomus grandis Boheman. The adsorbant, Porapak Q (ethylvinylbenzene-divinylbenzene), was utilized to trap and concentrate the pheromone. Captured pheromone was desorbed from columns packed with Porapak Q by elution withn-pentane and quantified by capillary column gas-liquid chromatography. In recovery studies with known amounts of synthetic grandlure, we found that the amount of each pheromone component collected was a function of collection duration, elution volume, and initial concentration. This effluvial method was capable of recovering as much as 94.9% of a known quantity (80 μg) of grandlure. The chromatograms were free of extraneous peaks. In studies of insect-produced pheromone, the effluvial method was used to collect pheromone from the air space surrounding male boll weevils as they fed on flower buds from CAMD-E cotton. The quantity and quality of boll-weevil-produced pheromone was determined for days 6, 8, 10, 11, 12, 13, and 14 of boll weevil adulthood. The maximum quantity of natural pheromone was produced on day 13 (4.2 μg/weevil) with a pheromone component ratio of 2.41∶2.29∶0.95∶1 for components I, II, III, and IV, respectively. The effluvial method described in this report is an efficient method to collect and quantify boll weevil pheromone from the atmosphere surrounding actively calling insects. Other applications of this method are suggested.     

Semiochemical-Mediated Location of Host Habitat by Apanteles carpatus (Say) (Hymenoptera: Braconidae), a Parasitoid of Clothes Moth Larvae

In Y-tube olfactometer bioassays, adult Apanteles carpatus (Say), were attracted to beaver or rabbit pelts infested with larvae of the casemaking clothes moth (CCM)Tinea pellionella L. Porapak Q-captured volatiles from a CCM-infested beaver pelt were also very attractive, whereas isolated CCM larvae or larval feces were not. Coupled gas chromatographic–electroantennographic detection (GC-EAD) analysis of the Porapak Q volatile extract revealed two compounds that elicited responses by A. carpatus antennae. Coupled GC–mass spectrometry (MS) in electron impact and chemical ionization modes of these compounds indicated, and GC-MS and GC-EAD of authentic standards confirmed, that they were nonanal and geranylacetone. While each compound singly did not attract A. carpatusa 1:1 blend of both compounds was as attractive as the volatile extract. Because these compounds are host habitat-derivedA. carpatus must be a habitat rather than host specialist, responding to kairomonal indicators of localized and specific habitats such as animal hair or feather. The tritrophic interaction between A. carpatusits clothes moth hosts and their animal-derived habitats is similar to the well-studied relationship between parasitoids of insect herbivores and their host plant habitats.     

Lanierone: A new pheromone component fromIps pini (Coleoptera: Scolytidae) in New York

A new pheromone component, lanierone, (2-hydroxy-4,4,6-trimethyl-2,5-cyclohexadien-1-one) was isolated and identified from a Porapak Q collection of volatiles from maleIps pini from New York through GC fractionation, bioassay, and spectrometry. In both the laboratory and the field, synthetic lanierone, in a 1:100 ratio with synthetic ipsdienol, is as attractive as natural pheromone sources. Synthetic ipsdienol alone is not attractive in the laboratory and only weakly attractive in the field. Varying the ratio of lanierone to ipsdienol in the field from 10^–41 to 11 in 10-fold increments resulted in an increased number of beetles trapped at the three lower ratios, but also in an increase in the proportion of males trapped. In the field, all combinations of lanierone to ipsdienol attracted proportionately fewer males than did pheromone-producing male beetles. GC and GC-MS analyses of Porapak Q-trapped volatiles revealed that lanierone is produced in an amount equal to about 0.2% of that of ipsdienol and is produced exclusively by males. The small amount of lanierone produced, together with a GC retention time similar to that of ipsdienol on a nonpolar column, probably confounded its detection in earlier studies.Deceased.     

Isolation of corn semiochemicals attractive and repellent to western corn rootworm larvae

Dichloromethane extracts of germinating corn are significantly attractive to western corn rootworm larvae in choice tests with equal levels of carbon dioxide present on both sides of the choice. Two fractions that are significantly attractive and two fractions that are significantly repellent to larvae were isolated from these extracts of germinating corn by gas chromatography and silica gel chromatography. In a separate set of experiments, Porapak N was used to collect headspace volatiles from germinating corn; significantly more larvae were attracted to aliquots of these extracts in singlechoice tests without added carbon dioxide present than to solvent controls.Coleoptera: Chrysomelidae.     

Moth Scale-Derived Kairomones Used by Egg–Larval Parasitoid Ascogaster quadridentata to Locate Eggs of Its Host, Cydia pomonella

We determined that location of host (Cydia pomonella) eggs by Ascogaster quadridentata is mediated by kairomones, investigated potential sources of the kairomones and identified a blend of kairomones from the source that was attractive to A. quadridentata. In Y-tube olfactometer bioassays, female A. quadridentata were attracted to Porapak Q-collected volatiles from female C. pomonella scales and eggs, but not to C. pomonella sex pheromone. Scales of C. pomonella were also attractive to male A. quadridentata. Coupled gas chromatographic–electroantennographic detection analysis of scale volatile extracts revealed numerous compounds that elicited responses from male or female A. quadridentata antennae, including heptanal, octanal, nonanal, decanal, undecan-2-one, dodecanal, pentadecan-2-one, (Z)-6-pentadecen-2-one, (Z)-9-hexadecenal, (Z)-6-heptadecen-2-one, and 3,7,11-trimethyl-2E,6E,10-dodecatrien-1-ol acetate. A synthetic blend of these compounds at quantities and ratios equivalent to Porapak Q scale volatile extract was attractive to female A. quadridentata in a Y-tube olfactometer bioassay.     

Pheromones in white pine cone beetle,Conophthorus coniperda (schwarz) (Coleoptera: Scolytidae)

Female white pine cone beetles,Conophthorus coniperda, attacking second-year cones of eastern white pine,Pinus strobus L., produced a sex-specific pheromone that attracted conspecific males in laboratory bioassays and to field traps. Beetle response was enhanced by host monoterpenes. The female-produced compound was identified in volatiles collected on Porapak Q and in hindgut extracts as (+)-trans-pityol, (2R,5S)-(+)-2-(1-hydroxy-1-methylethyl)-5-methyltetrahydrofuran. Males and females produced and released the (E)-(-)-spiroacetal, (5S,7S)-(-)-7-methyl-1,6-dioxaspiro[4.5]decane, which was not an attractant for either sex, but acted as a repellent for males. Porapak Q-trapped volatiles from both sexes contained (+)-trans-pinocarveol and (-)-myrtenol. In addition, hindgut extracts of females containedtrans-verbenol, while males had pinocarvone and verbenone. Work in Georgia and Canada confirmed that the same isomers of pityol and spiroacetal are present in two distinct and widely separated populations ofC. coniperda.     

Isolation and identification of two macrolide pheromones from the frass ofCryptolestes ferrugineus (Coleoptera: Cucujidae)

Two synergistic macrolide aggregation pheromones were isolated from Porapak Q-trapped volatiles obtained from the frass ofCryptolestes ferrugineus (Stephens). These compounds were identified as (E,E)-4,8-dimethyl-4,8-decadien-10-olide (I) and (3Z,11S)-3-dodecen-11-olide (II) and given the trivial names ferrulactone I and II, respectively. Analysis of captured volatiles from separated male and female adults disclosed that the pheromones are male-produced. Additional macrolides were identified in frass volatiles, but were devoid of any pheromonal activity. The structures of I and II were confirmed by comparison with synthetic materials.     

Sex pheromone of the San Jose scale

The sex pheromone of the San Jose scale,Quadraspidiotus perniciosus (Comstock), was isolated from airborne collections on Porapak Q. Two components, present in approximately equal amounts, were identified as (Z)-3,7-dimethyl-2,7-octadien-1-yl propanoate and 3-methylene-7-methyl-7-octen-1-yl propanoate. Greenhouse bioassays and field tests have shown that the compounds are independently attractive to male San Jose scale. These structures are compared with those of other known scale pheromones.     

气相色谱法测定贫富液组成

建立了用Tenax-TA和PorapakN两根柱子通过六通阀切换测定炼厂脱硫装置贫富液组成的气相色谱分析方法,用TCD检测器进行信号检测,数据利用Agilent的Chemstation工作站采集和输出。该方法操作简单,分析时间在10min以内。结果表明,方法回收率为97．14％～103．70％,相对标准偏差为0．23％～1．80％。该方法准确,快速,简便,分离效果好,适用于工厂常规分析。     

亚试剂固相萃取光度法测定水中微量铜的研究

依据亚铜试剂与铜(Ⅰ)的显色反应以及WatersPorapak○RSep Park固相萃取小柱对显色配合物的固相萃取性能,建立了一种测定水样中μg/L级铜离子的新方法,在pH=4.5HAc NaAc缓冲介质中,吐温 80存在下,亚铜试剂与铜(Ⅰ)反应生成2∶1稳定配合物,该配合物可用WatersPorapak○RSep Park固相萃取小柱富集,小柱上富集的配合物用乙醇(内含1%醋酸)洗脱后用吸光光度法测定,可用于水样中μg/L级铜离子的测定。该方法应用于几种水样中微量铜离子的测定,结果令人满意。