Combining 1,4-dimethoxybenzene, the major flower volatile of wild strawberry Fragaria vesca, with the aggregation pheromone of the strawberry blossom weevil Anthonomus rubi improves attraction

The aggregation pheromone of strawberry blossom weevil [Anthonomus rubi Herbst (Col.: Curculionidae)], a 1:4:1 blend of Grandlure I, II and racemic lavadulol, has been available for pest monitoring for several years but shows low attractancy. Attempts to control A. rubi using the pheromone alone were also unsuccessful. This paper reports the finding that addition of the major flower volatile from wild strawberry flowers [Fragaria vesca L. (Rosaceae)], 1,4-dimethoxybenzene (comprising 98% of the volatiles emitted from wild strawberry flowers), to the aggregation pheromone increased trap catches by over two fold compared to the pheromone alone. There was no significant difference between the response of overwintered or summer emerged adults. Field trials in 2007-2008 in central and southern Norway, Denmark and southern England used green funnel traps with white cross vanes for the evaluations. (-)-Germacrene D, previously shown to be emitted by plants in increased amounts in the presence of pheromone producing weevils, did not improve trap catches. Thus, the combined use of the aggregation pheromone and 1,4-dimethoxybenzene is promising for improved monitoring and possibly control of this important pest of strawberry

Syntheses and behaviour activity of conjugated polyenic pheromone components

This thesis deals with the synthesis of conjugated dienicand trienic pheromone components- C12-C16alcohols, acetates and aldehydes and theirapplications in pheromone communication studies. Insect pheromones are widely used in modern pest management.The development of effective tools for plant protection is aresult of complex broad, interdisciplinary basic and appliedresearch. A practical use of pheromones for pest managementusually requires that specific active chemicals must beisolated,identified and produced synthetically. The creationof pheromone materials besides requires the identification ofthe active components, determination of the roles of otherpossible isomers or degradation products, the design ofdispensers of suitable substrates and evaporationparameters. The aim of the thesiswas critically to survey methods for the syntheses ofconjugated polyenic compounds and to focus to the synthesis ofseveral conjugated polyenic pheromone components providingsufficient quantities of chemically and isomerically purecompounds for bioassaying. The principal objective of the thesiswas concerned withthe further aim of developing effective synthetic materials forplant protection. The work was focussed: =>To identify the compoundscollected from the leafminer mothPhyllonorycter emberizaepenella(Lepidoptera:Gracillaridae) and perform a detailed identification of thepheromones of the Brazilian apple leafrollerBonagota cranaodes(Meyrick) (Lepidoptera: Tortricidae)and of the codling mothCydia pomonella(L.) (Lepidoptera: Tortricidae). =>Tostudy the effect of non-pheromonal isomers of the mainpheromone component on the sex attraction of B. cranaodes andC.pomonellain wind tunnel and field tests.=>To study the role of identified pheromonecomponents in the pheromone communication of the currant shootborer Lampronia capitella (Cl.) (Lepidoptera: Prodoxidae), andto design and optimize the dispenser for effective trapping.=>To investigate the presence of sex pheromonecomponents in the tobacco hawk mothManduca sexta(L.) (Lepidoptera: Sphingidae). The syntheses of four geometrical isomers of3,5-dodecadienyl acetate; (10E,12E,14Z)- and(10E,12E,14E)-(10,12,14)-hexadecatrien-1-als;(E,Z)-, (Z,E)-,and (Z,Z)-8,10-dodecadienol, codlemone acetate and aldehyde;(9Z,11Z)-9,11-tetradecadienol, corresponding acetate andaldehyde; all geometrical isomers of 8,10-and10,12-tetradecadienols and corresponding acetates wereperformed to ensure all these bioassays with syntheticpheromone components. All compounds were made in high chemicaland stereochemical purity, most of them more than 99%isomerically pure or by using several separation andpurification techniques. The suitable synthetic schemes for the synthesis of all fourgeometrical isomers of four conjugated dienic pheromonecomponents are presented in this thesis. The reactions and purification methods used here exemplifythe wide range of possibilities realized for such syntheses:they present the successful application of many syntheticmethods. The importance of this synthetic work is that thecompounds synthesized are not commercially available or on theother hand the purity of the purchasable compounds is notsatisfactory for research in the field of chemical ecology. Key words:Lepidoptera, sex pheromone, pheromonedispenser, 3,5-dodecadienyl acetate, 10,12,14-hexadecatrienal,8,10-dodecadienol, codlemone atsetate, codlemone aldehyde,8,10- tetradecadienol, 8,10-tetradecadienyl acetate,10,12-tetradecadienol, 10,12-tetradecadienyl acetate,Lampronia capitella, Manduca sexta, Bonagota cranaodes,Cydia pomonella, Phyllonorycter emberizaepenella,conjugated polyenic pheromone, conjugated diene, MPLC,(9Z,11Z)-9,11-tetradecadien-1-ol,(9Z,11Z)-9,11-tetradecadien-1-a

Flight and molecular modeling study on the response of codling moth, Cydia pomonella (Lepidoptera : Tortricidae) to (E,E)-8,10-dodecadien-1-ol and its geometrical isomers

In a previous study we have reported that both (E,Z)-8,10-dodecadienol (E,Z) and (Z,Z) 8,10-dodecadienol (Z,Z) isomers inhibit the attraction of male codling moth, Cydia pomonella L. when added to (E,E)-8,10-dodecadienol (E,E) while the (Z,E)-8,10-dodecadienol (Z,E) isomer induces slight increase in the number of males attracted to the pheromone source. In the present study, we have tested the behavioral activity of the individual geometrical isomers E,Z; Z,E and Z,Z. A few number of codling moth males flew to the Z,E-isomer while the other two isomers (i.e. E,Z and Z,Z) did not elicit any upwind orientation. Analysis of the Right behavior to the E,E- and Z,E-isomer showed significant differences in most of the flight parameters evaluated. Based on the biological observations and molecular modeling, we suggest that the behavioral activity of the Z,E-isomer is due to presence of specific receptors for this isomer on male antennae and not to its structural resemblance to the E,E-isomer. These results underline the importance of the Z,E-isomer in sex attraction of male codling moth

Synthesis and anionic polymerization of isosorbide mono-epoxides for linear biobased polyethers

A series of regioisomeric isosorbide mono-epoxides, as well as diastereomerically pure mono-epoxy derivatives, have been prepared and studied. Anionic ring-opening polymerization of methoxy-capped monomers produced linear polyethers tethered with isosorbide units. These reasonably high molecular weight polymers exhibited glass transition temperatures at around 10-15 °C and thermal stability up to approximately 300 °C, which indicated that the mono-epoxides are promising building blocks for well-defined biobased polymers

Electrophysiological and behavioral responses to chocolate volatiles in both sexes of the pyralid moths Ephestia cautella and Plodia interpunctella

Volatiles from chocolate mediate upwind flight behavior in Ephestia cautella and Plodia interpunctella. We used gas chromatography with electroantennographic detection and found 12 active compounds derived from three different chocolate types, i.e., plain, nut-containing, and rum-flavored. Eight of the compounds were identified with mass spectrometry, and the activity of three compounds, ethyl vanillin, nonanal, and phenylacetaldehyde (PAA), was subsequently confirmed in both electrophysiological and behavioral assays. In the electroantennogram experiment, PAA and nonanal were consistently eliciting responses in both species and sexes. Ethyl vanillin was active in males of both species, and also in P. interpunctella females. E. cautella females showed no antennal activity in response to ethyl vanillin. All three volatiles were attractive to E. cautella males and P. interpunctella females in a flight tunnel. E. cautella females were significantly attracted only to ethyl vanillin. P. interpunctella males were attracted to PAA. Ethyl vanillin is a novel insect attractant, whereas both nonanal and phenylacetaldehyde mediate behavior in many insect species. A final experiment revealed that a blend of the three volatiles was required to induce landing in the flight tunnel bioassay, and that the landing rate was dependent on dose. The three-component blend attracted both sexes of P. interpunctella and females of E. cautella, whereas E. cautella males were not attracted

Syntheses, characterizations, and biological activities of tetradeca-4,8-dien-1-yl acetates as sex attractants of leaf-mining moth of the genus Phyllonorycter (Lepidoptera: Gracillariidae)

The four possible isomers of tetradeca-4,8-dien-1-yl acetate and corresponding alcohols were synthesized stereoselectively by synthetic routes employing Wittig coupling reaction for the preparation of (Z,E)- and (Z,Z)-isomers, and alkylation of terminal alkynes for the preparation of (E,E)- and (E,Z)- isomers as the key steps. Synthetic products were characterized by 13C- and 1H-NMR spectroscopy as well as mass-spectrometric methods. All four isomers gave distinctive mass spectra where m/z 81 fragments clearly dominated. Elution order, followed by retention index presented in parenthesis, of tetradeca-4,8- dien-1-ols was determined as (Z,Z) (2082.1), (Z,E) (2082.8), (E,E) (2083.1), and (E,Z) (2083.2) from unpolar SPB-1 column, and as (E,E) (2210.2), (Z,E) (2222.1), (E,Z) (2223.4), and (Z,Z) (2224.7) from polar DB-WAX column. The isomers of tetradeca-4,8-dien-1-yl acetates eluted in the order of (Z,Z) (2176.1), (Z,E) (2178.4), (E,Z) (2185.9), and (E,E) (2186.4) from SPB-1, and (Z,E) (2124.3), (E,E) (2157.7), (Z,Z) (2128.9), and (E,Z) (2135.9) from DB-WAX columns. Field-screening tests for attractiveness of tetradeca-4,8-dien-1-yl acetates revealed that (4Z,8E)-tetradeca-4,8-dien-1-yl acetate significantly attracted Phyllonorycter coryli and Chrysoesthia drurella males. (4E,8E)-Tetradeca-4,8- dien-1-yl acetate was the most efficient attractant for Ph. esperella and Ph. saportella males, and (4E,8Z)- tetradeca-4,8-dien-1-yl acetate was attractive to Ph. cerasicolella malesRoyal Institute of Technology, Stockholm, [email protected] Didžiojo universitetasŠvietimo akademij