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. 

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.

The enantiomers of the naturally occurring alkaloid dihydropinidine 1, potential antifeedants against the pine weevil, Hylobius abietis, were prepared by diastereoselective, dimethylzinc mediated addition of pinacolyl 2-propenylboronate 14 to nitrones (R)- and (S)-2-methyl tetrahydropyridine-N-oxide 3, prepared from d- and l-alanine, respectively.

Tannins are polyphenolic compounds found mainly in bark. When reacting with iron, they form strongly coloured complexes, which through contamination from the bark may induce a brightness decrease of mechanical pulps. Wood itself contains phenolic compounds, which can form coloured complexes with iron. We have investigated gallotannin as a model for metal-binding sites in the pulp. The behaviour of tannin-iron complexes in solution and in pulp has been studied. In aqueous solution, the tannin-iron complexes can be decolourised by the addition of diethylenetriaminepentaacetic acid (DTPA). The colour of the tannin-iron complexes was very pH-dependent. Thus in solution, these were decolourised at low pH and at high pH the spectral characteristics were changed substantially. We have studied the effects on brightness and heatinduced brightness loss of the impregnation of thermomechanical pulp (TMP) with 30 parts per million iron (ppm i.e. mg/kg) either as iron or tannin-iron as well as the possibility to decrease such effects by using various solvent extractions. The tannin-iron impregnation causes a decrease in ISO-brightness of approximately 3% and an increase in the light absorption coefficient (k) by approximately 2 m(2)/kg at the tannin-iron absorbance maximum. 565 run. These effects are approximately ten times higher than those observed for the Pulp only impregnated with iron. Extraction with 1% by weight of DTPA provides a way to reduce the brightness decrease induced by the tanniniron complexes and the observed decrease can be attributed to removal of iron from the pulp. Acid extraction was the most efficient way to reduce the iron content in the pulps and to decoulorise the tannin-iron impregnated pulp. However, after acid extraction of iron impregnated Pulps, new chromophores were evidently formed. Addition of the reducing agent, sulphite, to extractions had no effect on the iron removal or the brightness of the impregnated pulps. The heat-induced brightness loss is not influenced by the addition of tannin-iron or iron. The brightness loss caused by heat was lower for pulps extracted with DTPA.

Tannins are polymeric, phenolic constituents found in the bark of pine and spruce. When reacting with iron ions, tannins form strongly coloured complexes. Thus, the presence of bark in the mechanical pulping process leads to decreased brightness of the pulp. In order to evaluate the effects of the presence of iron on the properties of pulp, we have impregnated thermomechanical pulp (TMP) with 30 parts per million (ppm i.e. mg/kg) iron either as Fe3+ or as tannin-iron complexes and studied how such treatments affect bleachability and heat-induced brightness reversion. The bleaching agents studied are hydrogen peroxide and sodium dithionite. Treatment of the tannin-iron impregnated pulp with 1% by weight of diethylenetriaminepentaacetic acid (DTPA) before bleaching with 4% hydrogen peroxide almost eliminated the brightness loss caused by the impregnation. Such a treatment also removed all of the added iron from both the tannin-iron and FeCl3 impregnated pulps. Approximately 5% more of the added peroxide was required for oxidation of the tannins in the tannin-iron impregnated pulp. Contrary to what was observed with peroxide bleaching, dithionite bleaching did not reduce the amount of iron in the pulps. Instead, the added iron and tannin-iron negatively affected the dithionite bleaching, even if the pulps were extracted with DTPA before bleaching. It should therefore be advantageous to first bleach with peroxide, which removes most of the iron, and then with dithionite. Compared with dithionite, peroxide yields a more efficient bleaching. The reason for this is that the former reduces the light absorption coefficient, the k-value, more efficiently in the whole visible spectrum, whereas dithionite reduces it mainly at shorter wavelengths. In our experiments, the addition of tannin-iron or FeCl3 to the untreated pulp did not increase heat-induced brightness reversion. This is Supported by the fact that although extraction of the samples with DTPA before bleaching lowered the iron content slightly, it-did not affect the brightness reversion. The initial brightness reversion of the dithionite bleached pulps was larger than that observed for the peroxide bleached pulps.

The role of organic Synthesis in the Mistra-program Biosignal.

In modern organic chemistry the synthesis of chiral enantiopure compounds is an extremely important objective. To achieve this, biocatalysts have emerged as key tools. The broad reactivity of hydrolytic enzymes combined with their ability to discriminate between enantiomers make them ideal catalysts for resolving racemic organic compounds to provide enantiomerically enriched products. This chapter gives an overview of how the enantioselectivity of hydrolases can be exploited to furnish virtually enantiopure compounds via kinetic resolution of racemic compounds and desymmetrisation of symmetric compounds. Enantioselectivity and E-values are discussed. Reversibility of hydrolase-catalysed reactions and how it can be avoided by using various irreversible acyl donors as well as the determination and optimization of enantioselectivity are briefly discussed. The bulk of the chapter consists of selected examples of hydrolase catalysed reactions of some important classes of compounds. Thus the usefulness of hydrolase-catalyzed reactions is demonstrated by several examples of reactions in organic solvents of primary, secondary, tertiary alcohols, various amines, and acid derivatives.