Kristina Sjödin

Occurrence and correlations of monoterpene hydrocarbon enantiomers in Pinus sylvestris and Picea abies.

The relative amounts and enantiomeric compositions of monoterpene hydrocarbons in branch and trunk xylem, in needles, and in resin from apical buds in 18 Pinus sylvestris trees have been determined and compared with the terpene content in branch xylem and needles of Picea abies. Besides the high amount of (+)-3-carene, an excess of (+)-α-pinene has been found in P. sylvestris, whereas in P. abies (−)-α-pinene dominates over (+)-α-pinene. In P. sylvestris, clear positive correlations were found between (+)-α-pinene and (+)-camphene in the four tissues analyzed. Good positive correlations were also observed between (−)-α-pinene and (−)-camphene in the two types of xylem, between (+)-α-pinene and (+)-β-pinene in the resin, and between tricyclene and (−)-camphene in resin and needles. In P. abies, positive correlations were found between (+)-α-pinene and (+)-camphene in the branch xylem and between tricyclene and (−)-camphene as well as between (−)-α-pinene and (−)-camphene in the needles. Complex relationships between (−)-α-pinene and (−)-β-pinene were found both in the P. abies and in the P. sylvestris tissues. The importance of the enantiomeric composition of α-pinene for the host selection of Ips typographus, Tomicus piniperda, and Hylobius abietis is discussed.

Correlations between selected monoterpene hydrocarbons in the xylem of six Pinus (pinaceae) species

Summary. The compositions of 23 monoterpene hydrocarbons of six pine species (Pinus sylvestris,P. yunnanensis, P. armandii, P. tropicalis, P. cubensis and P. caribaea) were compared, using multivariate data analysis. Four of the six species were clearly different from the other species in a Principal Components Analysis (PCA) model, based on the relative amounts (selective normalization) of the monoterpenes. The correlation coefficients between constituents were determined separately for each species and the strongest correlations were found between (+)-α-pinene and (+)-camphene and between the corresponding (—)-enantiomers, in all species. This pattern, i.e. a good correlation in all species, was neither shown by the correlation of the structurally more similar (+)-α/β-pinenes, nor by the (—)-α/β-pinenes or within the enantiomeric pairs of α-pinene and β-pinene. For these pairs of monoterpenes, good correlations were found in some species. None of the species showed good correlations in all the investigated monoterpene pairs presented here. Correlations between monoterpenes in insect-attacked trees (P. cubensis and P. caribaea, attacked by Dioryctria horneana, and P. yunnanensis, attacked by Tomicus piniperda) were also determined. The results are discussed from chemotaxonomic and biosynthetic points of view.

Carvone and less volatile analogues as repellent and deterrent antifeedants against the pine weevil, Hylobius abietis

Abstract:  The monoterpenoid carvone (1) has been shown to have strong antifeedant effects on Hylobius spp. However, because of the high volatility of carvone, long‐time protection of conifer seedlings in the field using this compound has not been possible. We demonstrate, in several bioassay steps, that less‐volatile, heavier analogues retain their pre‐ingestive feeding inhibition activity in the large pine weevil, Hylobius abietis (L.) for a longer time. The first step in the evaluation of the biological activity of 12 carvone analogues was a micro‐assay, a choice test lasting 4 h. Compounds active at 100 nmol/cm2 were further dose–response tested to give the effective dose needed to inhibit feeding by 50% (ED50). Of the 14 compounds tested, including both carvone enantiomers, seven heavier analogues were active at low doses (had low ED50 values). As expected from their lower vapour pressure compared with carvone, the heavier analogues proved more resistant to evaporation before testing. Thus, whereas the effect of 8‐hydroxy‐p‐menth‐en‐6‐one 4 declined after 2 days, some of the compounds with high molar masses, such as the alkylhydroxymenthenones 6 and 8, retained a stable activity for 4 days. The retained activity at 4 days was strongly correlated to molecular mass and boiling point. When tested on natural material (host Pinus sylvestris L. twig sections for 48 h), the heavier analogues showed a rather low activity. Probably, the activity of the more volatile compound carvone (1) is due to a repellent effect (olfactory mode) rather than the deterrent effects (gustatory mode) of the heavier compounds. In agreement with the relatively low activity on twigs in the laboratory, the hydroxymenthenone 4 was not active in the field when tested for 2 months as a 1 : 9 mixture with a polar wax.

Formation of hemiacetal esters in lipase-catalysed reactions of vinyl esters with hindered secondary alcohols

Normally many lipases are efficient catalysts for the acetylation of alcohols with vinyl acetate. Unexpectedly, we found that some sterically hindered secondary alcohols react slowly to yield hem ...

Antifeedants and Feeding Stimulants in Bark Extracts of Ten Woody Non-host Species of the Pine Weevil, Hylobius abietis

Bark of ten woody species, known to be rejected as a food source by the pine weevil, Hylobius abietis, were sequentially extracted by a Soxhlet apparatus with pentane followed by methanol. Species were alder (Alnus glutinosa), aspen (Populus tremula), beech (Fagus sylvatica), guelder rose (Viburnum opulus), holly (Ilex aquifolium), horse chestnut (Aesculus hippocastanum), lilac (Syringa vulgaris), spindle tree (Evonymus europaeus), walnut (Juglans regia), and yew (Taxus baccata). Bark of each species was collected in southern Scandinavia during the summer. Resulting extracts were tested for antifeedant activity against the pine weevil by a micro-feeding choice assay. At a dose corresponding to that in the bark, methanol extracts from Aesculus, Taxus, Ilex, and Populus were antifeedant active, while pentane extracts of Aesculus, Fagus, Syringa, and Viburnum were stimulatory. Four known antifeedants against H. abietis, the straight-chained carboxylic acids, hexanoic and nonanoic acid (C6 and C9), carvone, and carvacrol were identified by gas chromatography (GC)–mass spectrometry (MS) in several extracts. The major constituents were identified and tested for feeding deterrence. The aromatic compounds benzyl alcohol and 2-phenylethanol are new non-host plant-derived feeding deterrents for the pine weevil. Additionally, two feeding stimulants, β-sitosterol and 5-(hydroxymethyl)-2-furaldehyde, were identified. One active methanol extract of Aesculus bark was sequentially fractionated by liquid chromatography, and major compounds were tentatively identified as branched alcohols and esters of hexanoic acid. Five commercially available hexanoate esters and two commercially available branched alcohols were identified as new active antifeedants. Both stimulatory and inhibiting compounds were found in the same extracts and co-eluted in the same or adjacent fractions. The mix of semiochemicals of opposite activity in each extract or fraction could explain the stimulatory-, inhibitory-, or sometimes neutral activity. Generally, such co-occurrence confounds the isolation of antifeedants.

Antifeedants against Hylobius abietis pine weevils: an active compound in extract of bark of Tilia cordata linden.

Linden (Tilia cordata) bark was shown to contain an antifeedant effective against the large pine weevil, Hylobius abietis. Soxhlet extraction of inner and outer bark resulted in an extract that showed antifeedant activity in a microfeeding assay. The extract was fractionated by chromatography on silica gel using gradient elution with solvents of increasing polarity. The content of the fractions obtained was monitored by thin layer- and gas chromatography. Fractions of similar chemical composition were merged. Two of the 17 fractions showed antifeedant activity in the microfeeding assay. Nonanoic acid was identified in both of these fractions. Subsequent testing in the microfeeding assay showed that nonanoic acid possessed strong antifeedant activity against H. abietis adults.

Nonanoic acid, other alkanoic acids and related compounds as antifeedants in Hylobius abietis pine weevils.

A medium‐length, straight‐chain alkanoic acid, nonanoic acid, is known from laboratory microassays to be an antifeedant in adults of the large pine weevil, Hylobius abietis (L.) (Coleoptera: Curculionidae). Our hypothesis was that we could find new, less volatile alkanoic acids or related compounds suitable for field application and with improved long‐term duration. Alkanoic acids of varying chain lengths (C6–C13) were tested for antifeedant activity in H. abietis adults. Microassay choice tests showed that straight‐chain (C6–C11) alkanoic acids were active. However, high activities were restricted to the (C6–C10) acids, with the C9 (nonanoic acid) at 4 µmol cm−2 being the most active one. In a no‐choice test on pine twigs, the antifeedant effect of C10 acid was lower than that of the C8 and C9 acids. In microassays, less volatile methyl‐branched alkanoic acids exhibited lower antifeedant activities than did the corresponding straight‐chain ones. However, the most active of the methyl‐branched acids, 2‐methyldecanoic acid, had an activity similar to that of nonanoic acid. Compounds related to nonanoic acid were either active (1‐nonanol), weakly active (nonanoic anhydride), or inactive (nonanal, sodium nonanoate). The anhydride was highly active in the microassay, but less active on twigs. The antifeedant effects of the straight chain (C8–C10) alkanoic acids against pine weevil feeding were tested in the field. In contrast to the results from the twig tests, the less volatile C10 acid was more active in the field for the protection of transplants on fresh clear cuts over a 3‐month period than both the C8 and C9 acids. Phytotoxic effects of the alkanoic acids were observed both in the field and in laboratory studies. If a protective layer of paraffin was applied to the stem prior to application of the alkanoic acids, these undesired side effects were reduced.