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- Anderbrant, Olle, et al.
(författare)
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Release of sex pheromone and its precursors in the pine sawfly Diprion pini (Hym., Diprionidae)
- 2005
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Ingår i: Chemoecology. - : Springer Science and Business Media LLC. - 0937-7409 .- 1423-0445. ; 15:3, s. 147-151
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Tidskriftsartikel (refereegranskat)abstract
- The first identification of a sex pheromone of a pine sawfly (Hymenoptera, Diprionidae) dates back almost thirty years. Since then, female-produced pheromones of over twenty diprionid species have been investigated by solvent extraction followed by separation and identification. However, no study has shown what the females actually release. Collection of airborne compounds using absorbtion on charcoal filter as well as solid phase microextraction (SPME) followed by analysis employing gas chromatography combined with mass spectrometry (GC-MS), revealed an unusual system in Diprion pini, in which the pheromone precursor alcohol, 3,7-dimethyl-2-tridecanol, is released together with acetic, propionic, butyric and isobutyric acids. The corresponding acetate, propionate and butyrate esters of 3,7-dimethyl-2-tridecanol were also found in the samples. All esters were electrophysiologically active, and the propionate and isobutyrate were attractive in trapping experiments. Based on these and earlier reported results, it seems that at least in part of its range, the pheromone response of D. pini is not very specific with regard to the functional group, as long as this is an ester.
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| 2. |
- Andersson, Fredrik, et al.
(författare)
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Synthesis of two (S)-indoline-based chiral auxiliaries and their use in diastereoselective alkylation reactions
- 2006
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Ingår i: Tetrahedron. - : Elsevier BV. - 0957-4166 .- 1362-511X. ; 17:13, s. 1952-1957
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Tidskriftsartikel (refereegranskat)abstract
- Two chiral auxiliaries, 2-[(S)-indolin-2-yl]propan-2-ol 1a and (S)-2-(2-methoxypropan-2-yl)indoline 1b, were synthesised from enantiomerically pure (S)-indoline-2-carboxylic acid 3. High diastereoselectivities in alkylations of enolates of the propanoylamides derived from the two auxiliaries are presented. Surprisingly, both auxiliaries induced the same selectivity at the newly created stereogenic centre. The benzyl bromide and n-butyl iodide alkylation reactions showed diastereomeric ratios that were moderate (81:19) to very good (96:4) and with very good yields (86-98%). When LiCl was used as an enolate coordinating agent, in the benzylation of the enolate from propanoylated auxiliary 1a, a very high crude diastereomeric ratio was obtained (99.7:0.3).
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| 4. |
- Hedenström, Erik, et al.
(författare)
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Sex pheromone of the pine sawfly, Gilpinia pallida: Chemical identification, synthesis, and biological activity
- 2006
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Ingår i: Journal of Chemical Ecology. - : Springer Science and Business Media LLC. - 0098-0331 .- 1573-1561. ; 32:11, s. 2525-2541
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Tidskriftsartikel (refereegranskat)abstract
- We present the identification of the sex pheromone in the pine sawfly, Gilpinia pallida, including analysis of the female pheromone content, male antennal response and attraction in the field, and synthesis of the most active pheromone component. Several 3,7-dimethyl-2-alkanols were identified from female whole-body extracts, including some compounds with a 2R configuration. This is the first observation of such compounds in a pine sawfly species. Antennae of male G. pallida responded strongly in electroantennograph (EAG) recordings to the (2S,3R,7R)-isomers of the propionates of 3,7-dimethyl-2-tridecanol, 3,7-dimethyl-2-tetradecanol, and 3,7-dimethyl-2-pentadecanol, as well as to the acetates of the tri- and pentadecanols (the acetate of the tetradecanol was not tested). The propionate of (2S,3R,7R)-3,7-dimethyl-2-tetradecanol caught more males in the field than the corresponding isomer of tri- or pentadecanol. We suggest that the (2S,3R,7R)-isomer of 3,7-dimethyl-2-tetradecanol is likely the main sex pheromone precursor in G. pallida, with a subsidiary role for the (2S,3R,7R)-isomer of the tridecanol. Preparation of highly pure (2R,3R,7R)- and (2S,3R,7R)-stereoisomers of 3,7-dimethyl-2-tetradecanol, including the biological active esters, was performed via chemoenzymatic methods and is described in detail.
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| 5. |
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| 7. |
- Liénard, Marjorie, et al.
(författare)
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Key biosynthetic gene subfamily recruited for pheromone production prior to the extensive radiation of Lepidoptera
- 2008
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Ingår i: BMC Evolutionary Biology. - : Springer Science and Business Media LLC. - 1471-2148. ; 8:270
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Tidskriftsartikel (refereegranskat)abstract
- Background Moths have evolved highly successful mating systems, relying on species-specific mixtures of sex pheromone components for long-distance mate communication. Acyl-CoA desaturases are key enzymes in the biosynthesis of these compounds and to a large extent they account for the great diversity of pheromone structures in Lepidoptera. A novel desaturase gene subfamily that displays Δ11 catalytic activities has been highlighted to account for most of the unique pheromone signatures of the taxonomically advanced ditrysian species. To assess the mechanisms driving pheromone evolution, information is needed about the signalling machinery of primitive moths. The currant shoot borer, Lampronia capitella, is the sole reported primitive non-ditrysian moth known to use unsaturated fatty-acid derivatives as sex-pheromone. By combining biochemical and molecular approaches we elucidated the biosynthesis paths of its main pheromone component, the (Z,Z)-9,11-tetradecadien-1-ol and bring new insights into the time point of the recruitment of the key Δ11-desaturase gene subfamily in moth pheromone biosynthesis. Results The reconstructed evolutionary tree of desaturases evidenced two ditrysian-specific lineages (the Δ11 and Δ9 (18C>16C)) to have orthologs in the primitive moth L. capitella despite being absent in Diptera and other insect genomes. Four acyl-CoA desaturase cDNAs were isolated from the pheromone gland, three of which are related to Δ9-desaturases whereas the fourth cDNA clusters with Δ11-desaturases. We demonstrated that this transcript (Lca-KPVQ) exclusively accounts for both steps of desaturation involved in pheromone biosynthesis. This enzyme possesses a Z11-desaturase activity that allows transforming the palmitate precursor (C16:0) into (Z)-11-hexadecenoic acid and the (Z)-9-tetradecenoic acid into the conjugated intermediate (Z,Z)-9,11-tetradecadienoic acid. Conclusion The involvement of a single Z11-desaturase in pheromone biosynthesis of a non-ditrysian moth species, supports that the duplication event leading to the origin of the Lepidoptera-specific Δ11-desaturase gene subfamily took place before radiation of ditrysian moths and their divergence from other heteroneuran lineages. Our findings uncover that this novel class of enzymes affords complex combinations of unique unsaturated fatty acyl-moieties of variable chain-lengths, regio- and stereo-specificities since early in moth history and contributes a notable innovation in the early evolution of moth-pheromones.
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| 8. |
- Lindström, Mona, et al.
(författare)
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Synthesis of diastereo- and enantiomerically pure anti-3-methyl-1,4-pentanediol via lipase catalysed acylation : Tetrahedron: Asymmetry
- 2005
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Ingår i: Tetrahedron: Asymmetry. - : Elsevier BV. - 0957-4166. ; 16:7, s. 1355-1360
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Tidskriftsartikel (refereegranskat)abstract
- Racemic trans-4,5-dimethylhydrofuran-2(3H)-one was synthesised from 5-methyl-furan-2(3H)-one, (alpha-angelica lactone). The key reaction in the synthesis was the 1,4-conjugate addition of an organocuprate to 5-methylfuran-2(5H)-one (beta-angelica lactone). Different types of organocuprates were tested with the highest anti:syn ratio of 99.4:0.6 being obtained by the use of a Gilman organocuprate reagent. The enantioselective acylation of racemic 3-methyl-pentan-1,4-diol, catalysed by a variety of lipases in organic media, was investigated. The highest enantioselectivity (E > 400) was obtained when Novozyme 435 was used as the catalyst at a water activity of a(w) similar to 0. Thus, both enantiomers, (3S,4R)- and (3R,4S)-3-methyl-pentan-1,4-diol, were obtained in very high diastereomeric (> 99% de) and enantiomeric purities (> 99.8% and > 97.4% ee, respectively).
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| 9. |
- Lyytikäinen-Saarenmaa, P, et al.
(författare)
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Monitoring the European pine sawfly with pheromone traps in maturing Scots pine stands
- 2006
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Ingår i: Agricultural and Forest Entomology. - : Wiley. - 1461-9555 .- 1461-9563. ; 8:1, s. 7-15
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Tidskriftsartikel (refereegranskat)abstract
- 1. During 1989-93, field studies were conducted in Finland to develop a method based on pheromone traps to monitor and forecast population levels of the European pine sawfly (Neodiprion sertifer Geoffr.) and tree defoliation. 2. Three traps per site were baited with 100 μg of the N. sertifer sex pheromone, the acetate ester of (2S,3S,7S)-3,7-dimethyl-2-pentadecanol (diprionol), in maturing pine stands in southern and central Finland. In addition, three different dosages (1, 10 and 100 μg) of the pheromone were tested in 1991-92. 3. The highest number of males was observed in traps baited with the highest dose. On average, there was a 10-fold increase in trap catch between lure doses. 4. Density of overwintering eggs was used to evaluate the effectiveness of pheromone traps in predicting sawfly populations. The proportion of healthy overwintering eggs was determined each year. A model based on the number of current shoots on sample trees, diameter at breast height and tree height was formulated to estimate eggs per hectare. 5. Linear regression analysis produced high coefficients of determination between number of males in traps and density of total eggs in the subsequent generation, when populations were at peak densities. The relationships were not significant for low population densities. The results indicate a risk of moderate defoliation when the seasonal trap catch is 800-1000 males per trap or higher.
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| 10. |
- Nieberding, Caroline. M., et al.
(författare)
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The Male Sex pheromone of the Butterfly Bicyclus anynana : Towards an Evolutionary Analysis
- 2008
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Ingår i: PLOS ONE. - : Public Library of Science (PLoS). - 1932-6203. ; 3:7, s. e2751-
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Tidskriftsartikel (refereegranskat)abstract
- Background: Female sex pheromones attracting mating partners over long distances are a major determinant of reproductive isolation and speciation in Lepidoptera. Males can also produce sex pheromones but their study, particularly in butterflies, has received little attention. A detailed comparison of sex pheromones in male butterflies with those of female moths would reveal patterns of conservation versus novelty in the associated behaviours, biosynthetic pathways, compounds, scent-releasing structures and receiving systems. Here we assess whether the African butterfly Bicyclus anynana, for which genetic, genomic, phylogenetic, ecological and ethological tools are available, represents a relevant model to contribute to such comparative studies.Methodology/Principal Findings: Using a multidisciplinary approach, we determined the chemical composition of the male sex pheromone (MSP) in the African butterfly B. anynana, and demonstrated its behavioural activity. First, we identified three compounds forming the presumptive MSP, namely (Z)-9-tetradecenol (Z9-14:OH), hexadecanal (16:Ald) and 6,10,14-trimethylpentadecan-2-ol (6,10,14-trime-15-2-ol), and produced by the male secondary sexual structures, the androconia. Second, we described the male courtship sequence and found that males with artificially reduced amounts of MSP have a reduced mating success in semi-field conditions. Finally, we could restore the mating success of these males by perfuming them with the synthetic MSP.Conclusions/Significance: This study provides one of the first integrative analyses of a MSP in butterflies. The toolkit it has developed will enable the investigation of the type of information about male quality that is conveyed by the MSP in intraspecific communication. Interestingly, the chemical structure of B. anynana MSP is similar to some sex pheromones of female moths making a direct comparison of pheromone biosynthesis between male butterflies and female moths relevant to future research. Such a comparison will in turn contribute to understanding the evolution of sex pheromone production and reception in butterflies.
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