Mid Sweden University

The success of mating disruption in relation to the area treated is discussed

The pine sawfly Diprion jingyuanensis Xiao and Zhang (Hymenoptera: Diprionidae) is a serious pest of Pinus tabulaeformis Carr. in the Shanxi, Gansu, and Inner Mongolia provinces in P. R. China. The sex pheromone of D. jingyuanensis was shown to be the propionate ester of 3,7-dimethyl-2-tridecanol. Virgin females contained an approximate 1:3 blend of the pheromone precursors erythro-(2S,3S,7R/S and 2R,3R,7R/S)-3,7-dimethyl-2-tridecanol and threo-(2S,3R,7R/S and 2R,3S,7R/S)-3,7-dimethyl-2-tridecanol, but the exact stereoisomers were not determined. Males responded the strongest to the propionate ester of the two threo-isomers, (2S,3R,7R) and (2S,3R,7S), in electroantennogram (EAG) recordings, followed by a significant EAG response to the (2S,3R,7R) propionate of diprionol (pheromone component of D. similis), whereas the remaining two isomers (2S,3S,7S and 2S,3S,7R) of the propionate ester of 3,7-dimethyl-2-tridecanol and the acetate of the (2S,3R,7R) isomer (one of the two pheromone components of D. pini) did not elicit any significant increase in antennal response. In the field, the strongly EAG-active (2S,3R,7R)-isomer alone was only weakly (but significantly) attractive to D. jingyuanensis males at 100 µg, while the equally EAG- active (2S,3R,7S)-isomer alone at the same loading was 8–14 times more attractive than was the (2S,3R,7R)-isomer alone. Traps baited with the same amounts of the two threo-isomers ((2S,3R,7R) and (2S,3R,7S), 100 µg + 100 µg) caught significantly more males than did traps baited with other isomers, either of the two isomers alone or other proportions of the two isomers. Thus, the (2S,3R,7S)-isomer is considered as a strong and essential sex-attractant component for D. jingyuanensis males, whereas the (2S,3R,7R)-isomer is a weak but synergistic sex-attractant. This is one of the few examples of a pine sawfly responding significantly stronger to a binary blend of stereoisomers in a synergistic fashion than to a single stereoisomer alone. 

Extracts of Diprion similis females contained about 15 ng of the sex pheromone precursor 3,7‐dimethylpentadecan‐2‐ol per female. After derivatisation with (S)‐2‐acetoxypropanoyl chloride, we found that the major stereoisomer in the extract was (2S,3R,7R)‐3,7‐dimethylpentadecan‐2‐ol. Small amounts of other stereoisomers of 3,7‐dimethylpentadecan‐2‐ol were also identified in the extract, namely 1% of (2R,3S,7S), 0.3% (2R,3R,7R) and 0.4% of (2R,3R,7S). An unknown fifth substance showed a very similar spectrum to 3,7‐dimethylpentadecan‐2‐ol, both in SIM and full scan mode. None of the earlier suggested behavioural synergistic isomers ((2S,3S,7S), (2S,3S,7R) and (2S,3R,7S)) were detected in the extracts. In field tests in Ontario, Canada, the earlier identified main pheromone component, viz. the propanoate of (2S,3R,7R)‐3,7‐dimethylpentadecan‐2‐ol, was tested alone and in combination with other stereoisomers, earlier reported to be synergistic. No synergistic effects were detected and the threo four‐isomer blend was as attractive as the pure main compound. Thus, one of the few examples of a diprionid sawfly using more than one substance in its sex pheromone could not be confirmed. The results also suggest that monitoring programs can use the more easily synthesized threo‐blend without losing efficiency. Furthermore, the study suggests that other diprionid pheromones may benefit from a reinvestigation, to clarify possible synergistic effects of stereoisomers. 

Extracts of Diprion similis females were found to contain about 15 ng of the sex pheromone precursor 3,7-dimethylpentadecan-2-ol per female. When analysing the extracts after derivatisation with (2S)-2-acetoxypropionyl chloride, we found that the major stereoisomer in the extract was (2S,3R,7R)-3,7-dimethylpentadecan-2-ol. Also other stereoisomers of 3,7-dimethylpentadecan-2-ol were identified in the extract namely, 1% of (2R,3S,7S) , 0.3% (2R,3R,7R) and 0.4% of (2R,3R,7S). An unknown fifth substance showed an identical spectrum to 3,7-dimethylpentadecan-2-ol, both in SIM and full scan mode. In field tests in Ontario, Canada, the earlier identified main pheromone component, viz. the propanoate of (2S,3R,7R)-3,7-dimethylpentadecan-2-ol, was tested alone and in combination with other stereoisomers, earlier reported to be synergistic. In none of the tests were any synergistic effects detected and the threo four-isomer blend was as attractive as the pure main compound. Thus, one of the few examples of a diprionid sawfly using more than one substance in its sex pheromone could not be confirmed. The results also suggest that monitoring programs can use the more easily synthesized threo-blend without losing efficiency.

The pine sawfly Neodiprion sertifer (Geoffroy) uses the acetate or propionate of (2S,3S,7S)-3,7-dimethyl-2-pentadecanol (diprionol) as pheromone components, with the (2S,3R,7R)-isomer being antagonistic, synergistic, or inactive according to the population tested. In this study, we tested the attraction of males to the acetates of three analogs of diprionol, each missing one methyl group, viz. (2S,7S)-7-methyl-2-pentadecanol, (2S,6S)-2,6-dimethyl-1-tetradecanol, and (2S,3S)-3-methyl-2-pentadecanol. None of the analogs alone, or in combination with diprionol acetate, was attractive in Sweden, even at 100 times the amount of diprionol acetate attractive to N. sertifer. In Japan, the acetate of (2S,3S)-3-methyl-2-pentadecanol attracted males when tested in amounts 10–20 times higher than the acetate pheromone component. The acetate esters of the (2S,3R)-analog and the (2S,3R,7R)-isomer of diprionol also were tested in combination with the pheromone compound (acetate ester). Both compounds caused an almost total trap-catch reduction in Sweden, whereas in Japan they appear to have relatively little effect on trap capture when added to diprionol acetate. Butyrate and iso-butyrate esters of diprionol were unattractive to N. sertifer in Sweden. In summary, there exists geographic variation in N. sertifer in responses to both diprionyl acetate and some of its analogs.

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.

Alkylation of the enolates of the propanoylamides of two chiral auxiliaries (S)-(-)-2-(pyrrolidin-2-yl)propan-2-ol 1a and (S)-(-)-2-(2-methoxypropan-2-yl)pyrrolidine 1b, derived from (S)-proline, with benzyl bromide and n-butyl iodide has been studied. The auxiliaries 1a and 1b induced opposite selectivity that is (R)- and (S)-configuration, respectively, at the newly created stereogenic centre. The diastereoselectivities and conversion yields in these alkylations were moderate to excellent. When Cp2ZrCl2 was used as an enolate coordinating agent, benzylation of propanoylated 1b gave an excellent diastereomeric ratio of 99:1. The benzylated diastereomeric products from either propanoylated 1a or 1b were easily separated by liquid chromatography.

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).

The rare beetle Elater ferrugineus was sampled at 47 sites in the county of Östergötland, Sweden by means of pheromone-baited traps to assess its value as an indicator species for hollow oak stands rich in rare saproxylic beetle species. In addition, Osmoderma eremita was also sampled with pheromone baits. These data were then compared against species survey data collected at the same sites by pitfall and window traps. Both species co-occur with many Red Listed saproxylic beetles, with E. ferrugineus being a somewhat better indicator for the rarest species. The conservation value of a site (measured as Red List points or number of Red Listed species) increased with the number of specimens of E. ferrugineus and O. eremita caught. Accuracy of sampling by means of pheromone trapping turned out to be radically different for the two model species. E. ferrugineus traps put out during July obtained full accuracy after only 6. days, whereas O. eremita traps needed to be out from early July to mid-August in order to obtain full accuracy with one trap per site. By using E. ferrugineus, or preferably both species, as indicator species, accuracy would increase and costs decrease for saproxylic biodiversity sampling, monitoring and identification of hotspots. © 2014 Elsevier Ltd.

Decentralized composting is an emerging method for managing biowaste, engaging waste generators as active recyclers in the waste management cycle. Evaluating performance and identifying optimization opportunities within this composting framework is essential to maximize its benefits and address its challenges. In small-scale composters, fresh waste is continuously mixed with previously added materials, shifting the typical composting process. As with larger systems, the composition of the feedstock influences the temperature profile and the quality of the final product. The issue of whether to include animal-source waste remains controversial in the development of standards and program guidelines. On the other hand, evaluating a leachate recycling method could help prevent nutrient loss and mitigate environmental impacts when bulking agents are lacking. In this study, kitchen and garden wastes were composted in 500-L static composters under cold climate conditions. We examined obtained compost stability, maturity, and quality parameters to determine the effects of adding animal by-product waste and/or recycling leachate. Our findings indicate that including animal by-products allows reaching sanitation temperatures under cold weather conditions and that recycling leachates could reduce nutrient losses and alleviate environmental and other user concerns while improving temperature, stability, maturity, and product quality patterns in decentralized composting. 

(Z)-4-undecenal (Z4-11Al) is the volatile pheromone produced by females of the vinegar fly Drosophila melanogaster. Female flies emit Z4-11Al for species-specific communication and mate-finding. A sensory panel finds that synthetic Z4-11Al has a characteristic flavour, which can be perceived even at the small amounts produced by a single female fly. Since only females produce Z4-11Al, and not males, we can reliably distinguish between single D. melanogaster males and females, according to their scent. Females release Z4-11Al at 2.4 ng/h and we readily sense 1 ng synthetic Z4-11Al in a glass of wine (0.03 nmol/L), while a tenfold concentration is perceived as a loud off-flavour. This corroborates the observation that a glass of wine is spoilt by a single D. melanogaster fly falling into it, which we here show is caused by Z4-11Al. The biological role of Z4-11Al or structurally related aldehydes in humans and the basis for this semiochemical convergence remains yet unclear. 

We have identified the existence of different modes of binding the enantiomers of 2-methyl-branched carboxylic acids to a lipase active site by rational substrate engineering. Similar to hydrolysis, previously investigated, we have now evidence for differential binding modes in the Candida rugosa lipase-catalyzed esterifications in cyclohexane. The relevance of considering two different binding modes to understand lipase enantiorecognition is demonstrated by introducing bulky substituents on a chiral carboxylic acid which impose a different orientation of the substrate acyl chain in the active site of Candida rugosa lipase. With this substrate engineering approach based on molecular modeling it is thus possible to markedly alter the enantioselectivity of the lipase. Examples from hydrolysis and new results from esterifications in an organic solvent are presented and discussed.

Conditional stability constants of coordination complexes comprising divalent transition metals, Cu2+, Ni2+, Zn2+, Co2+, and ethylenediaminetetraacetic acid (EDTA) were determined utilizing electrospray ionization mass spectrometry. The deviation of signal response of a reference complex was monitored at addition of a second metal ion. The conditional stability constant for the competing metal was then determined through solution equilibria equations. The method showed to be applicable to a system where Co2+ and Zn2+ competed for EDTA at pH 5. When Cu2+ and Ni2+ competed for EDTA, the equilibrium changed over time. This change was shown to be affected in rate and size by the type of organic solvent added. In this work, 30% of either methanol or acetonitrile was used. It was found that if calibration curves are prepared for both metal complexes in solution and the measurements are repeated with sufficient time space, any change in equilibrium of sample solutions will be discovered. Copyright © 2014 John Wiley & Sons, Ltd. Copyright © 2014 John Wiley & Sons, Ltd.

In this work, we continue our study of methyl -substituted surfactants and present the aqueous binary phase diagrams of racemic sodium 2-methyloctanoate, -nonanoate, and -dodecanoate, respectively. All systems have very low Krafft temperatures within the solution phase, between 1 and 4 degreesC. The phase sequences of the two shorter surfactants are very similar to those of the unsubstituted sodium octanoate, although with somewhat different range of existence for the phases formed. The sodium 2-methyldodecanoate system is different from the unsubstituted sodium dodecanoate system, as the former seems to lack a hexagonal phase. The surfactant systems were delineated using H-2 NMR splittings and crossed polarizers, and combined with SAXS for determination of phase structure. 

Stereoisomers of long-chain secondary alcohols are used as sex pheromone precursors among pine sawflies, which can be severe pest to conifers. To use the pheromone in environmentally friendly pest managements, methods are needed that can determine the exact stereochemistry of the precursor alcohols. Combinations of 11 acid chloride derivatives and 10 GC columns were evaluated for separation of the stereoisomers of 3,7-dimethylundecan-2-ol, 3,7-dimethyldodecan-2-ol, 3,7-dimethyltridecan-2-ol, 3,7-dimethyltetradecan-2-ol, and 3,7-dimethylpentadecan-2-ol. Derivatisation with (2S)-2-acetoxypropionyl chloride in combination with the Chiraldex B-PA column separated all eight stereoisomers of 3,7-dimethylundecan-2-ol, 3,7-dimethyldodecan-2-ol and 3,7-dimethyltridecan-2-ol. A combination of two different derivatisation methods was needed to separate all stereoisomers of the longer chained alcohols, 3,7-dimethyltetradecan-2-ol and 3,7-dimethylpentadecan-2-ol. An extract of the pine sawfly Neodiprion lecontei was also analysed, and the stereochemistry of the sex pheromone alcohol prcursor was determined to be (2S,3S,7S)-3,7-dimethylpentadecan-2-ol, at an amount of about 7 ng/female. This paper presents the first GC-MS-separation of all eight stereoisomers of 3,7-dimethylundecan-2-ol, 3,7-dimethyldodecan-2-ol and 3,7-dimethyltridecan-2-ol in a single analytical run, and also the first determination of the stereochemistry of the sex pheromone precursor of N. lecontei.

A GC-MS method to analyze the stereoisomeric composition of chiral secondary alcohols found in whole body extracts of pine sawfly females was developed. The tested alcohols were derivatized with optically pure (S)-2-acetoxypropionyl chloride prior to GC-MS analysis. Baseline separation was obtained for all sixteen stereoisomers of 3,7,9-trimethyltridecan-2-ol and for the four 3-methylpentadecan-2-ol stereoisomers. For 3,7-dimethyltridecan-2-ol, 3,7-dimethyltetradecan-2-ol and 3,7-dimethylpentadecan-2-ol baseline separation was obtained for 6 of the possible 8 stereoisomers. When a mixture of 16 stereoisomers of 3,7,11-trimethyltridecan-2-ol was tested, baseline separation of 7 peaks out of 16 possible was obtained. The investigated alcohols are pheromone precursors for some pine sawfly species that are severe defoliators of pine. Females from several Diprion, Neodiprion, Macrodiprion, Microdiprion, and Gilpinia species emit esters of such secondary alcohols as sex pheromones that attract males for mating. To quantify the small amounts of the precursor alcohol and its stereoisomeric composition found in whole body extracts from female pine sawflies, a purification method was optimized. An extract of 20 females of D. pini contained about 8 ng of (2 S,3 R,7 R)-3,7-dimethyltridecan-2-ol per female, and three extracts of 18, 20, and 90 females of N. sertifer contained between 5 and 13 ng of (2 S,3 S,7 S)-3,7-dimethylpentadecan-2-ol per female.

The European grapevine moth, Lobesia botrana, uses (E,Z)-7,9-dodecadienyl acetate as its major sex pheromone component. Through in vivo labeling experiments we demonstrated that the doubly unsaturated pheromone component is produced by increment 11 desaturation of tetradecanoic acid, followed by chain shortening of (Z)-11-tetradecenoic acid to (Z)-9-dodecenoic acid, and subsequently introduction of the second double bond by an unknown increment 7 desaturase, before final reduction and acetylation. By sequencing and analyzing the transcriptome of female pheromone glands of L. botrana, we obtained 41 candidate genes that may be involved in sex pheromone production, including the genes encoding 17 fatty acyl desaturases, 13 fatty acyl reductases, 1 fatty acid synthase, 3 acyl-CoA oxidases, 1 acetyl-CoA carboxylase, 4 fatty acid transport proteins and 2 acyl-CoA binding proteins. A functional assay of desaturase and acyl-CoA oxidase gene candidates in yeast and insect cell (Sf9) heterologous expression systems revealed that Lbo_PPTQ encodes a increment 11 desaturase producing (Z)-11-tetradecenoic acid from tetradecanoic acid. Further, Lbo_31670 and Lbo_49602 encode two acyl-CoA oxidases that may produce (Z)-9-dodecenoic acid by chain shortening (Z)-11-tetradecenoic acid. The gene encoding the enzyme introducing the E7 double bond into (Z)-9-dodecenoic acid remains elusive even though we assayed 17 candidate desaturases in the two heterologous systems.

Fiberbanksfrom the pulp and paper industry are typically contaminated with a wide range ofchlorinated aromatic and aliphatic toxins such as HCB and other chlorinated benzenes, PCB,HCH, DDT, PCDD, PCDF and Chlorophenols. This poses a formidable challenge for theanalyst to develop appropriate analytical methodology for the monitoring of the progress ofremediation.In preparation to this undertaking, an examination of a practical analytical method using oneextraction method, one clean-up and one analysis method for the aforementioned targetcompounds found in the fibrous sediment. This method was performed using acceleratedsolvent extraction (ASE), a modified silica gel column and GC-FID/ECD. 

Additionally,an assessment of the levels of organic pollutants was conducted,with the purposeofmeasuringthe potential alteration in contaminantswhenfreeze-drying, air-drying andautoclavingpretreatments are applied to the sediment samples, prior to be used as a media forbiological remediation.The results showed that the ASE is a very fast and reliable method of extraction, with yieldscomparableorhigher than the reference Soxhlet extraction method. Theactivatedsilica gelcolumn demonstrated adequate purification of the sediment extract for analysisusingthe twodetectors, FID and ECD, whichwere able to identify the target analytes fromonlyone purifiedextract. The method employed in this study has the potentialto reduceboth processing timeand materialusedfor analytical sample preparation. Lastly, some modifications inconcentrations anddistribution of target analyteswere revealedin thesediments pre-treated byautoclave and air-driedwhencompared withthefreeze-dried sediments, which can helpunderstanding the development of the biological remediation process.

6,10,14-Trimethylpentadecan-2-one (Hexahydrofarnesyl acetone; HHA) previously has been found to be a major component in tibial fragrances of male orchid bees, Euglossa spp. HHA is a chiral molecule with four possible stereoisomers, (6R,10R)-, (6R,10S)-, (6S,10R)-, and (6S,10S)-6,10,14-trimethylpentadecan-2-one. In the present study, we characterized HHA extracted from Euglossa as the pure enantiomer (6R,10R)-6,10,14-trimethylpentadecan-2-one. During bioassays in Mexico and Panama, the synthetic RR-isomer attracted males of six species of orchid bees, including three that were known to contain HHA in their tibial fragrances. Possible sources of HHA for wild bees are flowers of euglossophilous orchids and aroids. With a molecular weight of 268, HHA is the largest natural molecule known to attract male orchid bees in pure form. Its attractiveness to males suggests that low-volatility compounds have a function in male signals, e.g., serve as a "base note" in complex odor bouquets. © 2010 Springer Science+Business Media, LLC.

Norway spruce (Picea abies) debarking water is an aqueous extract obtained as waste from the debarking of logs at paper mills. The debarking water contains a mixture of natural compounds that can exhibit diverse biological activities, potentially including fungicidal activity on some species of wood-decaying fungi. Thus, we investigated the growth rates of such fungi on agar plates to which debarking water extracts had been added. The experiment included five wood-decaying fungi, viz. Gloeophyllum sepiarium, Oligoporus lateritius, Ischnoderma benzoinum, Junghuhnia luteoalba, and Phlebia sp. Growth reduction was observed for all species at the highest tested concentrations of freeze-dried and ethanol-extracted debarking water, the ethyl acetate-soluble fraction and the diethyl ether-soluble fraction. However, the magnitude of the effect varied between different species and strains of individual species. The brown-rot fungi G. sepiarium and O. lateritius were generally the most sensitive species, with the growth of all tested strains being completely inhibited by the ethyl acetate-soluble fraction. These results indicate that development of antifungal wood-protecting agents from debarking water could potentially be a way to make use of a low-value industrial waste.

All living things speak chemistry. The challenge is to reveal the vocabulary, the odorants that enable communication across phylogenies and to translate them to physiological, behavioral, and ecological function. Olfactory receptors (ORs) interface animals with airborne odorants. Expression in heterologous cells makes it possible to interrogate single ORs and to identify cognate ligands. The cosmopolitan, anthropophilic strain of the vinegar fly Drosophila melanogaster depends on human resources and housing for survival. Curiously, humans sense the pheromone (Z)-4-undecenal (Z4-11Al) released by single fly females. A screening of all human ORs shows that the most highly expressed OR10A6 is tuned to Z4-11Al. Females of an ancestral African fly strain release a blend of Z4-11Al and Z4-9Al that produces a different aroma, which is how we distinguish these fly strains by nose. That flies and humans sense Z4-11Al via dedicated ORs shows how convergent evolution shapes communication channels between vertebrate and invertebrate animals. 

Fiberbanks refer to a type of fibrous sediment originated by the forestry and wood pulping industry in Sweden. These anthropogenic sediments are significantly contaminated with potentially toxic elements, and a diverse array of organic pollutants. Additionally, these sediments are of environmental concern due to their potential role in greenhouse gas emissions. Given the environmental risks posed by these sediments, the development of effective remediation strategies is of critical importance. However, no specialized methods have been established yet for the cleanup of this specific type of contaminated sediments. To identify effective fungal species for the mycoremediation of the fiberbank substrate, we performed a detailed screening experiment. In this research, we primarily aimed at assessing both the growth capacity and the proficiency in degrading organic pollutants of 26 native white-rot fungi (WRF) species. These species were sourced from natural forest environments in northern Sweden. The experimental setup involved evaluating the WRF on plates containing fiberbank material with a central Hagem-agar disc to closely monitor the interaction of these species with fiberbank substrates. Among the fungi tested, Laetiporus sulphureus exhibited the highest growth area percentage at 72%, followed by Hymenochaete tabacina at 68% and Diplomitoporus crustulinus at 67%. For the removal of 2–3 ring polycyclic aromatic hydrocarbons (PAHs), Phellinus punctatus led with 68%, with Cystostereum muraii at 57% and Diplomitoporus crustulinus at 49%. Regarding the removal percentage of 4–6 ring PAHs, Diplomitoporus crustulinus showed the highest efficiency at 44%, followed by Phlebia tremellosa at 40% and Phlebiopsis gigantea at 28%. 

Background: Sex pheromones are essential in moth mate communication. Information on pheromone biosynthetic genes and enzymes is needed to comprehend the mechanisms that contribute to specificity of pheromone signals. Most heliothine moths use sex pheromones with (Z)-11-hexadecenal as the major component in combination with minor fatty aldehydes and alcohols. In this study we focus on four closely related species, Heliothis virescens, Heliothis subflexa, Helicoverpa armigera and Helicoverpa assulta, which use (Z)-11-hexadecenal, (Z)-9-tetradecanal, and (Z)-9-hexadecenal in different ratios in their pheromone blend. The components are produced from saturated fatty acid precursors by desaturation, β-oxidation, reduction and oxidation. Results: We analyzed the composition of fatty acyl pheromone precursors and correlated it to the pheromone composition. Next, we investigated whether the downstream fatty-acyl reduction step modulates the ratio of alcohol intermediates before the final oxidation step. By isolating and functionally characterizing the Fatty Acyl Reductase (pgFAR) from each species we found that the pgFARs were active on a broad set of C8 to C16 fatty acyl substrates including the key pheromone precursors, Z9-14, Z9-16 and Z11-16:acyls. When presenting the three precursors in equal ratios to yeast cultures expressing any of the four pgFARs, all reduced (Z)-9-tetradecenoate preferentially over (Z)-11-hexadecenoate, and the latter over (Z)-9-hexadecenoate. Finally, when manipulating the precursor ratios in vitro, we found that the pgFARs display small differences in the biochemical activity on various substrates. Conclusions: We conclude that a pgFAR with broad specificity is involved in heliothine moth pheromone biosynthesis, functioning as a semi-selective funnel that produces species-specific alcohol product ratios depending on the fatty-acyl precursor ratio in the pheromone gland. This study further supports the key role of these in pheromone biosynthesis and emphasizes the interplay between the pheromone fatty acyl precursors and the Lepidoptera specific pgFARs in shaping the pheromone composition. © 2012 Hagström et al.

Polluted land in marginalized regions, such as tropical low-incomecountries and sparsely populated regions in industrialised countries, demand specialremediation strategies that are energy-efficient, locally adapted, economicallyviable. Strategies for appropriate bioremediation technology under such circumstancescan be based on locally available resources in combination with in situbioremediation technologies to keep energy and material costs down. A pilot scaleexperiment was set up to test the application of three organic by-products from thelocal industry (whey, pyroligneous acid and compost tea) to enhance the naturalbiodegradation of diesel in ultisol. Biweekly applications of 6 mL whey kg−1 soilsignificantly increased the degradation rate but no positive effect on degradationwas found with any of the other amendments. Tropical climate is favourable forbiodegradation but many tropical soils are rich in clay which can inhibit the bioavailabilityof the pollutant which in turn may be decisive for biodegradation kinetics. If low cost is a crucial factor, our results indicate that whey treatment has the potential to be an appropriate technology for treating petroleum-contaminated soils in tropical regions.

Lignocellulose-bearing sediments are legacies of the previously unregulated wastewater discharge from the pulp and paper industry, causing large quantities of toxic organic waste on the Baltic Sea floor and on the bottom of rivers and lakes. Several km2 are covered with deposits of lignocellulosic residues, typically heavily contaminated with complex mixtures of organic and inorganic pollutants, posing a serious threat to human and ecological health. The high toxicity and the large volume of the polluted material are challenges for remediation endeavours. The lignocellulosic material is also a considerable bioresource with a high energy density, and due to its quantity, it could appeal to commercialization as feedstock for various marketable goods. This study sets out to explore the potential of using this polluted material as a resource for industrial production at the same time as it is detoxified. Information about modern production methods for lignocellulosic material that can be adapted to a polluted feedstock is reviewed. Biochemical methods such as composting, anaerobic digestion, as well as, thermochemical methods, for instance, HTC, HTL, pyrolysis, gasification and torrefaction have been assessed. Potential products from lignocellulose-bearing sediment material include biochar, liquid and gaseous biofuels, growing substrate. The use of a contaminated feedstock may make the process more expensive, but the suggested methods should be seen as an alternative to remediation methods that only involve costs. Several experiments were highlighted that support the conception that combined remediation and generation of marketable goods may be an appropriate way to address polluted lignocellulose-bearing sediments. Graphic abstract: [Figure not available: see fulltext.] 

Fiberbanks and fiber-rich sediments are legacies of the previously unregulated wastewater discharge from the pulp and paper industry that have accumulated large quantities of toxic organic waste on the Baltic Sea floor and on the bottom of rivers and lakes. Several km2 are covered with deposits of fibrous residues that are, typically, heavily polluted with a number of organic and inorganic substances, posing a serious threat to human and ecological health. High toxicity and the large volume of the polluted material are challenges for remediation endeavors. However, since the fibrous material is a bioresource with a high energy density, the sheer quantity of it could appeal to commercialization as feedstock for various marketable products. This study sets out to explore the potential of using this polluted material as a resource for industrial production, by reviewing and synthesizing data about modern production methods or reuse alternatives for lignocellulose material that can be adapted to a polluted feedstock. Biochemical methods such as composting, anaerobic digestion, as well as, thermochemical methods, for instance, HTC, HTL, pyrolysis, gasification etc. have been assessed. Potential end products from fiber bank material include biochar, liquid and gaseous biofuels, growth media, and fatty acids and proteins produced by white-rot fungi.

The use of pheromones to determine distributions of rare saproxylic insects is an increasingly popular technique. Pheromones may, however, also be used to elucidate the biology of these cryptic species, a vital requirement if they are to be accurately monitored and conserved. We used non-invasive aerial trapping to compare the effectiveness of chemicals produced by Elater ferrugineus L (Coleoptera: Elateridae), namely 7-methyloctyl (Z)-4-decenoate (the female-produced sex pheromone), and male compounds (geranyl and neryl acetone and 6-methyl-5-heptene-2-one). The male compounds were identified using headspace analysis by solid phase micro-extraction gas chromatography-mass spectrometry. We discovered that males only produce these two compounds after having been attracted to a female, and that this serves to attract further males to a female. Such compounds do not appear to attract females but for a species that has a short activity period and is non-feeding in the adult stage, may ensure breeding success when populations are low. By marking all beetles caught, we were able to demonstrate that recapture rate using this method is low (approximately 11% of total captures annually). Therefore, the method does not limit dispersal or breeding opportunities, making it a valuable tool for monitoring endangered saproxylic beetle species.

To date, conservation-status saproxylic beetle species in the UK have been monitored by chance findings or by monitor-based observational studies. Here, using Elater ferrugineus as our target species, we present the first national distribution survey carried out in the UK or across mainland Europe on such a species using chemicals produced by the insect. Over 3 years, mark-release-recapture studies were performed across the UK, using 416 lured (pheromone) traps monitored by volunteer recorders; the first survey in Europe to do so. Traps were baited with 7-methyloctyl- (Z)-4-decenoate, a compound previously identified as a female sex pheromone. The results were used to plot a distribution map and investigate factors that may influence the distribution, including summer temperatures, possible habitat availability and larval food source. The survey revealed a south-eastern distribution of E. ferrugineus in the UK, which was suggested by previous casual studies. A correlative model was fitted to the data, indicating that 55% of the variation in the distribution of E. ferrugineus was explained by climatic variables (temperature and wind speed).

3,7-Dimethyl-2-undecanol, 3,7,9-trimethyl-2-tridecanol, and 3,7, 11-trimethyl-2-tridecanol were synthesized as racemic mixtures in moderate yields. The alcohols are known precursors of the female sex pheromones of the pine sawfly species Diprion nipponica, Macrodiprion nemoralis, and Microdiprion pallipes, respectively. Stereoisomeric mixtures of 3,8,12-trimethyl-2-tridecanol, erythro-(2R,3R,11R/S)-3,11-dimethyl-2-tetradecanol, 3,5-dimethyl-2-tetradecanol, and 5,7-dimethyl-2-tetradecanol, structurally related to sex pheromone alcohol precursors of pine sawfly species, were also synthesized in moderate yields. The key reaction in the syntheses was the ring opening of γ-butyrolactones by using different alkyl lithiums as nucleophiles.

The N-propionylated pyrrolidine derivative and chiral auxiliary, (S)-(-)-2-(pyrrolidin-2-yl)propan-2-ol, was synthesised and used in stereoselective aldol reactions with benzaldehyde. Differences in stereoselectivity were investigated as a function of temperature, solvent, chelating agent and the amount of the chelating agent used by monitoring the ¹H NMR spectra of the aldol adducts that were obtained. Among the additives that were investigated, Cp₂ZrCl₂ induced higher syn-selectivity, while SnCl₂ induced higher syn-selectivity respectively. TMSCl was found to induce high selectivity for one syn- and one anti-diastereomer. Varying the ligand sets on titanium additives was found to induce differences in selectivity, with (i-PrO)₃TiCl exhibiting syn-selectivity and Cp₂TiCl₂ exhibiting anti-selectivity. Differences in reactivity and stereoselectivity were also found to depend upon the amount of Lewis acid that was added. Methods for removal of the auxiliary were also investigated. Acidic hydrolysis was used successfully to obtain the desired 3-hydroxy-2-methyl-3-phenylpropionic acids, but was found to give low yields and resulted in a large amount of epimerisation. Furthermore, the ethyl esters of these hydroxy acids are easy to separate into pure syn- and anti-diastereomers by LC. © The Royal Society of Chemistry 2000.

Male neotropical orchid bees (Euglossini) collect volatiles from varied sources in their environment to compile complex, species-specific tibial perfumes, which are later released at mating sites. A major compound prominent in tibial extracts of Euglossa allosticta was purified, as well as isolated and its structure was elucidated by analytical methods including GC–MS, GC–FTIR, HRMS and 1H and 13C NMR. After synthesis, the compound with the proposed structure was finally identified as 6-(4-methylpent-3-en-1-yl)naphthalene-1,4-dione. At field sites in Panama and Costa Rica, the synthetic compound attracted males of E. allosticta, but no other euglossines. This strengthens the view that semivolatiles play an important role in conveying specificity to perfume signals of orchid bees. 

The immobilised Candida rugosa lipase (CRL) displayed S-preference for both stereogenic centres in this sequential esterification of 2,6-dimethyl-1,7-heptanedioic acid (1) (pure meso and meso: (+/-) mixture, 53/47) with n-butanol in cyclohexane at a(w) = 0.8. The reaction was faster when short-chain primary n-alcohols was used and very slow, or even none reactive, when a Ion-chain alcohol was used.

Several 3-methylalkan-2-ols precursors to sex pheromones of Diprion pini, Gilpinia pallida, Gilpinia frutetorum, Diprion nipponica, Macrodiprion nemoralis and Microdiprion pallipes were synthesised as stereoisomeric mixtures in moderate to good yields. The key reaction sequence in the syntheses was the ring opening of either cis- or racemic trans-epoxybutane using a higher order cyanocuprate as nucleophile followed by a highly efficient lipase catalysed stereoselective acylation of the obtained 3-methylalkan-2-ol. The biologically active species specific stereoisomer was synthesised as a single stereoisomer in high stereoisomeric purity, as one in a mixture of two or as one of four stereoisomers when the appropriate 3-methylalkan-2-ol was stereoselectively acylated using a Pseudomonas sp. lipase as catalyst.

3,7-Dimethylpentadecan-2-ol and 3-methylpentadecan-2-ol were identified in female whole body extracts from the two pine sawfly species Gilpinia frutetorum and Gilpinia socia. This is the first observation of 3-methylpentadecan-2-ol in extracts of a female pine sawfly species. Synthetic and highly pure stereoisomers of 3,7-dimethylpentadecan-2-ol and 3-methylpentadecan-2-ol were used to verify that the (2S,3R,7R)-isomer of 3,7-dimethyl- pentadecan-2-ol and (2S,3R)-3-methylpentadecan-2-ol were present in the extracts. The four stereoisomers of 3-methylpentadecan-2-ol and their biologically active esters were produced via chemoenzymatic methods and the synthesis is described in detail. Male G. socia anten- nae responded strongly in EAG recordings to the (2S,3R)-isomer of the acetate and propionate of 3-methylpentadecan-2-ol. Male antennae of both G. frutetorum and G. socia also responded to the (2S,3R,7R)- and (2S,3R,7S)-acetates of 3,7-dimethylpentadecan-2-ol.