Sex pheromone analysis and effective attraction of males of the cabbage webworm,Hellula undalis,inhabiting the Mekong Delta of Vietnam

Hellula undalis is a harmful insect pest of green mustard in the Mekong Delta of Vietnam. In order to establish a tool for a sustainable pest control program, the sex pheromone of H. undalis inhabiting the Mekong Delta was examined. GC-EAD and GC–MS analyses of pheromone gland extracts from the virgin females elucidated three new components, (Z)-11-tetradecenyl acetate (Z11-14:OAc), (Z)-11-hexadecenal (Z11-16:Ald), and (11E,13E)-11,13-hexadecadien-1-ol, in addition to the known pheromone component (11E,13E)-11,13-hexadecadienal (E11,E13-16:Ald). Double bond positions of the two monoenyl components were determined by GC–MS analysis of the pheromone extract treated with dimethyl disulfide. On the other hand, GC–MS analysis of the female body extract detected the unsaturated hydrocarbon (3Z,6Z,9Z)-3,6,9-tricosatriene (Z3,Z6,Z9-23:H). Field examinations of their synthetic compounds indicated the significant role of E11,E13-16:Ald as a major component and a clear synergistic effect of the two monoenyl compounds as a minor component. Although the 3:3:7 mixture of Z11-14:OAc, E11-16:Ald, and E11,E13-16:Ald captured the largest number of males among the tested mixtures, the activity was still quite a bit lower than that of virgin females. However, the 3:3:7:1 mixture, which was prepared by adding a small amount of Z3,Z6,Z9-23:H to the 3:3:7 ternary lure, succeeded in attracting males more powerfully than the females did. This strong synergistic effect was not observed when the triene was added to unmixed E11,E13-16:Ald, indicating important roles of not only the triene but also the two monoenyl compounds as natural pheromone components.     

A two-component sex attractant for males of the geometrid moth Alsophila quadripunctata

The binary mixture of the hydrocarbons (3Z,6Z,9Z)-3,6,9-nonadecatriene and (6Z,9Z)-6,9-nonadecadiene is a sex attractant for males of Alsophila quadripunctata Esp. (Lepidoptera, Geometridae). Triene/diene ratios from 1:1 to 1:0.01 attracted males in the field, the ratios 1:1 and 1:0.7 were most effective. The triene on its own also attracted males, but in significantly lower numbers than the 1:1 mixture. In a dosage test the highest dose, 1800 g of 1:0.8 [triene:diene] mixture applied to rubber caps was most effective. This is the first report of a geometrid sex attractant with field activity containing more than one component.

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Zusammenfassung Die binäre Mischung der Kohlenwasserstoffe (3Z,6Z,9Z)-3,6,9-Nonadecatrien [ZZZ3,6,9-19:H] und (6Z,9Z)-6,9-Nonadecadien [ZZ6,9-19:H] in den Verhältnissen 1:1 bis 1:0.01 erwies sich im Freiland als Sexuallockstoff für Männchen von Alsophila quadripunctata (Geometridae, Lepidoptera). Dabei besaß die 1:1-Mischung die beste Fängigkeit, das Nonadecatrien allein lockte schlechter, während das C₁₉-Alkadien unwirksam war. Ein Dosiswirksamkeitstest ergab bei Köderbeladungen von 1.8 mg (Trien:Dien + 1:0.8) die besten Fangergebnisse. Im Verlauf der Untersuchungen wurden weitere zwölf geometrische-oder positionsisomere C₁₉-Polyenkohlenwasserstoffe getestet, wobei keine der geprüften Verbindungen Attraktant-oder Inhibitorwirkung zeigte.

     

槐庶尺蛾性信息素腺体EAG活性成分绝对构型的鉴定(英文)

槐庶尺蛾Semiothisa cinerearia Bremer et Grey （鳞翅目： 尺蛾科）是我国北方国槐Sophora japonica L.上的重要食叶害虫。本研究的主要目的是阐明槐庶尺蛾性信息素成分化学结构的绝对构型, 为在城市地区环境友好地防控槐庶尺蛾的为害提供一种新方法。经与标准品比较气相色谱保留时间和质谱特征离子, 从槐庶尺蛾处女雌蛾（2-3日龄）性信息素腺体溶剂提取物中检测到顺6, 顺9-顺-3, 4-环氧-十七碳二烯烃和顺3, 顺6, 顺9-3, 6, 9-十七碳三烯烃2种成分, 在腺体中以100∶4.8±1.3 （N=12）的比例存在。槐庶尺蛾性信息素腺体提取物进一步经手性毛细管色谱柱（CycloSil-B, 30 m×0.25 mm×0.25 μm 液膜厚）分离, 在优化的程序升温条件下发现腺体成分顺6, 顺9-顺-3, 4-环氧-十七碳二烯烃具有3R, 4S的绝对构型。两种合成的对映异构体混合物顺6, 顺9-3R, 4S-环氧-十七碳二烯烃和顺6, 顺9-3S, 4R-环氧-十七碳二烯烃以1.28∶1的比例加到腺体提取物中, 比例变为1.55∶1。根据这一分析, 腺体成分顺6, 顺9-顺-3, 4-环氧-十七碳二烯烃进一步确认具有3R, 4S的绝对构型。该研究结论将为生产上研发高效的槐庶尺蛾性信息素诱芯奠定坚实的基础。     

Conformational Changes of αs-Casein by Heating

Conformational changes of α_s-casein by heating were investigated by measuring ultraviolet difference spectra. The ultraviolet difference spectra at elevated temperature against 5.5°C were measured in various ionic strengths and pHs. Thermal effects of the difference spectra were cancelled by comparing with the spectra of model compounds such as lysozyme and ribonuclease, and the blue shift of α_s-casein spectra was observed at above 30°C in these all experimental conditions. This shift was considered to mean unfolding of the α_s-casein molecule. The aggregation of α_s-casein was observed above ionic strength of 0.4 by heating. These heat-induced changes were reversible until the aggregation was observed.     

Sex pheromone of the butterbur borer, Ostrinia zaguliaevi

The sex pheromone blend of the butterbur borer, Ostrinia zaguliaevi (Lepidoptera: Pyralidae) was analyzed by means of gas chromatography-electroantennographic detection (GC-EAD), GC-mass spectrometry and a series of wind-tunnel bioassays. Four EAD-active compounds were detected in the female sex pheromone gland extract, and these were identified as tetradecyl acetate (14:OAc), (Z)-9-tetradecenyl acetate (Z9-14:OAc), (E)-11-tetradecenyl acetate (E11-14:OAc) and (Z)-11-tetradecenyl acetate (Z11-14:OAc). The average amounts ± s.d. of the four compounds in a single sex pheromone gland were 7.9±3.7 ng, 10.1±3.2 ng, 1.1±0.5 ng and 11.6±5.1 ng, respectively. In a wind-tunnel bioassay, the ternary blend of Z9-, E11- and Z11-14:OAc at a ratio found in the sex pheromone gland (45:5:50) elicited the same behavioral responses from the males as did virgin females and pheromone gland extract. Removal of any single compound from the ternary blend significantly diminished the pheromonal activity, whereas addition of 14:OAc to the ternary blend had no effect on the males' behavioral responses. Therefore, it was concluded that the sex pheromone blend of O. zaguliaevi is composed of Z9-14:OAc, E11-14:OAc and Z11-14:OAc at a ratio of 45:5:50.     

Sex pheromone of Etiella behrii, a pod borer of soybean in Indonesia: identification and field attraction

Four EAG-active components were detected in GC-EAG analyses of hexane extracts from virgin Etiella behrii (Zeller) (Lepidoptera: Pyralidae) females. These components were identified as dodecyl acetate (12:Ac), (E)-9-dodecenyl acetate (E9-12:Ac), either (Z)-9- or (E)-11-tetradecenyl acetate (Z9- or E11-14:Ac), and (Z)-11-tetradecenyl acetate (Z11-14:Ac) by comparison of retention indices on both nonpolar and polar GC columns. The available extract was insufficient for further GC-MS or other chemical analyses (<0.2 ng/female). In field tests carried out in East Java, a 10:90 mixture of E9-12:Ac and Z11-14:Ac showed attractiveness to male moths and addition of 12:Ac and/or E11-14:Ac significantly increased the trap catches while addition of Z9-14:Ac showed no significant effect. Maximum attraction was obtained with 5.35 or 10.7 g/rubber septum of a mixture of E9-12:Ac, Z11-14:Ac, 12:Ac and E11-14:Ac at the ratio of 10:90:0.7:6.3, respectively. The role of pheromone blends in species discrimination between E. behrii and the related E. zinckenella (Treitschke) is discussed.     

Sex pheromone components ofHeliothis maritima: chemical identification, flight tunnel and field tests

Three sex pheromonal components, (Z)-11-hexadecenal (Z11–16:Ald), (Z)-11-hexadecenol (Z11–16:OH), and hexadecanal (16:Ald), in a ratio of 88.0∶7.2∶4.8, were identified from ovipositor extracts of the fulvous clover moth,Heliothis maritima Grasl. (Lepidoptera: Noctuidae) by gas chromatographymass spectrometry. In addition, trace amounts of (Z)-9-hexadecenal (Z9–16:Ald) were detected in the extracts by GC. A blend of Z11–16:Ald, Z11–16:OH and 16:Ald in a ratio of 100∶6∶3, as well as in combination with 0.1 or 1 part Z9–16:Ald was tested at 0.01, 0.1, 1.0 and 10.0 μg doses in a flight tunnel. In flight tunnel tests male behavioral responses elicited by 0.1 or 1.0 μg doses of the 100∶6∶3∶1 blend were similar to those elicited by an ovipositor extract at 2 female equivalents. Deletion of Z9–16:Ald from the blend at 0.1 μg dose caused a decrease in the male response. In the field test, however, presence or absence of Z9–16:Ald did not significantly influence the number of males trapped in sticky traps with rubber septa containing 100 μg of the respective blends.     

Optimization of pheromone lure and trap design for monitoring the fir coneworm, Dioryctria abietivorella

The major components of the sex pheromone of Dioryctria abietivorella (Groté) (Lepidoptera: Pyralidae) were recently identified as (9Z,11E)‐tetradecadien‐1‐yl acetate (9Z,11E‐14:Ac) and a polyunsaturated, long‐chain hydrocarbon (3Z,6Z,9Z,12Z,15Z)‐pentacosapentaene (C25 pentaene). The optimal ratio of these components and the role of potential minor components were not fully determined in the initial short report on the pheromone's identification. We tested different ratios of the two major components loaded into grey halobutyl rubber septum dispensers, placed in sticky traps deployed in conifer breeding arboreta. The optimal ratio of the two components was 200 µg 9Z,11E‐14:Ac to 2000 µg C25 pentaene. (Z)‐9‐Tetradecen‐1‐yl acetate, which had been identified previously in female pheromone gland extracts, and five other potential minor pheromone components, were tested individually as additions to the optimized two‐component lure blend. None of the ternary blends were more attractive than the optimized two‐component blend, at the ratios tested. Two lure adjuvants, a UV stabilizer (Sumisorb 300) and the antioxidant butylated hydroxytoluene, added individually or together, did not affect the attractiveness of the optimized lure blend. The Pherotech diamond sticky trap baited with the optimized lure blend was the most effective trap design among eight types of sticky trap and a bucket style trap that were tested. Traps baited with synthetic lures were as attractive as traps baited with virgin female moths. The optimized two‐component lure blend in the Pherotech diamond trap is recommended for monitoring fir coneworm infestations. The availability of an effective synthetic pheromone opens the possibility for control tactics using mating disruption or attract‐and‐kill techniques.     

Isolation and Structural Determination of the Antifouling Diketopiperazines from Marine-Derived Streptomyces praecox 291-11

Marine derived actinomycetes constituting 185 strains were screened for their antifouling activity against the marine seaweed, Ulva pertusa, and fouling diatom, Navicula annexa. Strain 291-11 isolated from the seaweed, Undaria pinnatifida, rhizosphere showed the highest antifouling activity and was identified as Streptomyces praecox based on a 16S rDNA sequence analysis. Strain 291-11 was therefore named S. praecox 291-11. The antifouling compounds from S. praecox 291-11 were isolated, and their structures were analyzed. The chemical constituents representing the antifouling activity were identified as (6S,3S)-6-benzyl-3-methyl-2,5-diketopiperazine (bmDKP) and (6S,3S)-6-isobutyl-3-methyl-2,5-diketopiperazine (imDKP) by interpreting the nuclear magnetic resonance and high-resolution mass spectroscopy data. Approximately 4.8 mg of bmDKP and 3.1 mg of imDKP were isolated from 1.2 g of the S. praecox 291-11 crude extract. Eight different compositions of culture media were investigated for culture, the TBFeC medium being best for bmDKP and TCGC being the optimum for imDKP production. Two compounds respectively showed a 17.7 and 21 therapeutic ratio (LC₅₀/EC₅₀) to inhibit zoospores, and two compounds respectively showed a 263 and 120.2 therapeutic ratio to inhibit diatoms.     

Field evaluation of female sex pheromone of the artichoke moth, Gortyna xanthenes

Field responses of Gortyna xanthenes (Germar) males to traps baited with different mixtures of the female sex pheromone components were evaluated in an artichoke field. Catches were compared to those obtained by virgin females and light traps. The best results were achieved by utilizing a mixture of 5 mg Z11-16:Ald + 0.15 mg Z9-16:Ald + 0.15 mg 16:Ald + 0.12 mg Z11-16:OH, which captured only G. xanthenes males 3–5 times more than light traps and ca two times more than one virgin female. Starting from the basic mixture Z11-16:Ald (89–92%) + Z9-16:Ald (2–4%), the addition of 16:Ald (2–4%) and of Z11-16:OH (2–3%) produced an increase of G. xanthenes and a decrease of H, armigera (Hb.) catches. The inhibitory action of Z11-16:OH towards H. armigera males was confirmed.

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Evaluation sur le terrain des constituants de la phéromone sexuelle de la noctuelle de l'artichaut (Gortyna xanthenes)

Résumé Dans un champ d'artichaut de la province de Salerno on a evalué la réponse des mâles de G. xanthenes à mélanges divers des constituants de la phéromone sexuelle produite par la femelle. Les meilleurs résultats ont été obtenus en employant un mélange de 5 mg Z11-16:Ald + 0.15 mg Z9-16:Ald + 0.15 mg 16:Ald + 0.12 mg Z11-16:OH, qui a capturé seulement les mâles de G. xanthenes en mesure 3–5 fois plus élevée que les pièges lumineux et ca. deux fois plus élevée que la femelle vierge. En partant du mélange base Z11-16:Ald (89–92%) + Z9-16:Ald (2–4%), l'addition de 16:Ald (2–4%) et de Z11-16:OH (2–3%) a causé un accroissement des captures de G. xanthenes et une diminution des captures de Heliothis armigera. Cela confirme l'action inhibitoire du Z11-16:OH à l'égard des males de H. armigera.

     

中国印度谷螟性信息素次级组份的研究

印度谷螟是我国危害性较严重的仓储害虫之一,食性很广,几乎危害每一种植物性仓储物.印度谷螟雌虫性信息素主要成份顺9,反12-十四碳二烯醇醋酸酯(TDA)早已被鉴定,并利用TDA单一组份诱捕印度谷螟雄蛾也较为有效,但该虫的完整信息素系统尚不清楚.本研究采用单个雌蛾性信息素腺体抽提技术,利用毛细管气相色谱GC保留时间定性方法和气质联用GC-MS分析鉴定技术,从印度谷螟雌虫腺体提取物中鉴定了顺9,反12-十四碳二烯醇醋酸酯(A),顺9,反12-十四碳二烯醇(B),顺9,反12-十四碳二烯醛(C)和顺9-十四碳醋酸醋(D)4种主要信息素成份,其比例为A∶B∶C∶D=100∶22∶12∶9.风洞试验结果表明,以该4种主要成分按A∶B∶C∶D=8∶2∶1∶0.8比例配制成的诱芯,其引诱雄蛾的活性接近于雌蛾腺体提取物.     

Components of the sex pheromone of the currant pug moth, Eupithecia assimilata, a re-emergent hop pest in UK

After an absence of 50 years, the currant pug moth, Eupithecia assimilata Doubleday (Lepidoptera: Geometridae), has reappeared as an important pest of hops, Humulus lupulus L. (Cannabaceae), in the UK. Pheromone gland extracts from virgin female E. assimilata moths were shown to contain (3Z,6Z)‐cis‐9,10‐epoxyheneicosadiene (3Z,6Z‐cis‐9,10‐epoxy‐21:H) by gas chromatography linked to mass spectrometry. (3Z,6Z,9Z)‐heneicosatriene (3Z,6Z,9Z‐21:H) was also found as a minor component in one of two extracts. In field experiments, significant numbers of male E. assimilata moths were caught in traps baited with the (9S,10R)‐enantiomer of 3Z,6Z‐cis‐9,10‐epoxy‐21:H but not in those baited with the (9R,10S)‐enantiomer or racemic mixture. Addition of 3Z,6Z,9Z‐21:H at the ratio present in gland extracts greatly reduced the attractiveness of the epoxydiene.     

Synthesis of (3E, 5Z)-3,5-Dodecadienylacetate,the Sex Pheromone of Phtheochroa cranaodes (Lepidoptera: Tortricidae)

(3E, 5Z)-3,5-Dodecadienyl acetate, the female sex pheromone of Phtheochroa cranaodes, was regio and stereo-selectively synthesized from 1-octyne and (E)-4-bromo-3-buten-1-ol by using Pd(PPh₃)₄, CuI and piperidine to afford the enyne (5). Further elaboration afforded the target pheromone. The synthetic pheromone was identified with the natural product by its MS and IR, data GLC retention time and biological activity.     

蛾类昆虫雄性信息素及其功能

昆虫性信息素是两性通讯系统的基础,其中雄性信息素的研究相对较少。本文综述了蛾类昆虫雄性信息素的研究进展。迄今已鉴定出40余种蛾类昆虫的雄性信息素,其行为学功能主要有对雌性的引诱和激欲、对同种雄性的抑制及种间隔离等。     

Mate location in the green capsid bug, Lygocoris pabulinus

Headspace extracts from female Lygocoris pabulinus (L.) (Heteroptera: Miridae) as well as female leg extracts attracted male L. pabulinus in Y‐track olfactometer bioassays. In contrast, only female leg extracts were active in the vibration bioassay. Male extracts had no activity at all in either bioassay. When the female leg extract was analysed by coupled gas chromatography‐electroantennography (Z)‐9‐pentacosene and (Z)‐7‐pentacosene were EAD‐active. (Z)‐9‐Pentacosene and sometimes (Z)‐7‐pentacosene were also observed in female headspace extracts. EAG responses could be obtained for (Z)‐9‐pentacosene. A mixture of (Z)‐9‐pentacosene and (Z)‐7‐pentacosene in the ratio 5 : 1 elicited vibration behaviour in males. The results indicate that these alkenes are important cues for male L. pabulinus in mate location behaviour.     

Electrophysiological and behavioural evidence for a fourth sex pheromone component in the turnip moth, Agrotis segetum

Abstract. In addition to the pheromone components (Z)-5-decenyl, (Z)-7-dodecenyl and (Z)-9-tetradecenyl acetate (Z5-10:OAc, Z7-12:OAc and Z9-14:OAc), it has previously been shown that the sex pheromone gland of the turnip moth, Agrotis segetum (Lepidoptera: Noctuidae Schiff) contains 10:OAc, 12:OAc, Z5-12:OAc, Z9-12:OAc, 11–12:OAc, Z5-14:OAc, Z7-14:OAc and Z11-16:OAc. To find out whether any of these additional compounds is involved in the sex pheromone communication in A. segetum, a comprehensive electro-physiological and behavioural investigation was conducted. Single-sensillum recordings on male antennae revealed three subtypes of sensilla among the previously so-called Z5-10:OAc sensilla. One subtype was identified having one receptor neurone (A) that responded to Z5-10:OAc with a large spike amplitude and another neurone (B) that responded to (Z)-5-decenol (Z5-10:OH) with a small spike amplitude. In another subtype the B neurone responded to Z5-12:OAc and sometimes also to 27-12:OAc and 10:OAc, in addition to responding to Z5-10:OH. In a third subtype the A neurone responded to all acetates identified from the female pheromone gland, whereas the small spike amplitude neurone was tuned to Z5-10:OH. A flight tunnel assay showed that blends composed of nine, eight or seven compounds were equivalent to the previously identified three-component pheromone blend in eliciting male behavioural responses. In field trapping tests, blends of eleven, nine or seven compounds did, however, catch significantly more moths than the three-component blend. Further assays showed that only 25- 12:OAc could significantly increase the catch numbers when added to the three-component blend, and thus qualified as a fourth pheromone component in A. segerum. The behavioural significance of additional female-produced acetates — for which males possess antennal receptors — is suggested, but may be impossible to confirm because of ‘diminishing returns’ when trying to refine a multicomponent pheromone further.     

A sex pheromone component novel to the Geometridae identified fromEpirrita autumnata

(Z,Z,Z)-1,3,6,9-Heneicosatetraene was identified as a sex pheromone component ofEpirrita autumnata (Borkhausen), (Lepidoptera: Geometridae). Gas chromatography coupled with electroantennographic detection revealed one active peak from female pheromone gland extracts. The chemical identification of the compound was based on gas chromatography-mass spectrometry, chemical micro-reactions and unambiguous synthesis. In a field test, a rubber septum loaded with 3000 μg of this compound showed highest attraction of maleE. autumnata moths compared to lower doses and the control. The attraction of males to a 300 μg bait was equivalent to that obtained using live virgin females.     

Male-specific (Z)-9-tricosene stimulates female mating behaviour in the spider Pholcus beijingensis

Chemical signals play an important role in spider sexual communication, yet the chemistry of spider sex pheromones remains poorly understood. Chemical identification of male-produced pheromone-mediating sexual behaviour in spiders has also, to our knowledge, not been reported before. This study aimed to examine whether chemically mediated strategies are used by males of the spider Pholcus beijingensis for increasing the probability of copulation. Based on data from gas chromatography–mass spectrometry analysis, electroantennography assay and a series of behavioural tests, we verified that (Z)-9-tricosene is a male-specific compound in the spider P. beijingensis. This compound acts as an aphrodisiac: it increases the likelihood that a female will mate. Mate-searching males release (Z)-9-tricosene to stimulate sexual behaviour of conspecific females. In the two-choice assay, however, sexually receptive females show no preference to the chambers containing (Z)-9-tricosene. This indicates that the male pheromone of P. beijingensis is not an attractant per se to the conspecific females. This is, to our knowledge, the first identification of a male-produced aphrodisiac pheromone in spiders.