The sex pheromones of two pine sawfly species, Gilpinia frutetorum and Gilpinia socia: chemical identification, synthesis and biological activity.

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-dimethylpentadecan-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 antennae 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.

Bayesian analysis of the species-specific lengthening of the growing season in two European countries and the influence of an insect pest.

A recent lengthening of the growing season in mid and higher latitudes of the northern hemisphere is reported as a clear indicator for climate change impacts. Using data from Germany (1951-2003) and Slovenia (1961-2004), we study whether changes in the start, end, and length of the growing season differ among four deciduous broad-leaved tree species and countries, how the changes are related to temperature changes, and what might be the confounding effects of an insect attack. The functional behaviour of the phenological and climatological time series and their trends are not analysed by linear regression, but by a new Bayesian approach taking into account different models for the functional description (one change-point, linear, constant models). We find advanced leaf unfolding in both countries with the same species order (oak > horse chestnut, beech, and birch). However, this advance is non linear over time and more apparent in Germany with clear change-points in the late 1970s, followed by marked advances (on average 3.67 days decade(-1) in the 2000s). In Slovenia, we find a more gradual advance of onset dates (on average 0.8 days decade(-1) in the 2000s). Leaf colouring of birch, beech, and oak has been slightly delayed in the last 3 decades, especially in Germany, however with no clear functional behaviour. Abrupt changes in leaf colouring dates of horse chestnut with recent advancing onset dates can be linked across countries to damage by a newly emerging pest, the horse chestnut leaf-miner (Cameraria ohridella). The lengthening of the growing season, more distinct in Germany than in Slovenia (on average 4.2 and 1.0 days decade(-1) in the 2000s, respectively), exhibits the same species order in both countries (oak > birch > beech). Damage by horse chestnut leaf-miner leads to reduced lengthening (Germany) and drastic shortening (Slovenia) of the horse chestnut growing season (-12 days decade(-1) in the 2000s). Advanced spring leaf unfolding and lengthening of the growing season of oak, beech and birch are highly significantly related to increasing March temperatures in both countries. Only beech and oak leaf unfolding in Germany, which is generally observed later in the year than that of the other two species, is more closely correlated with April temperatures, which comparably exhibit marked change-points at the end of the 1970s.

Sex pheromone of the pine sawfly, Gilpinia pallida: chemical identification, synthesis, and biological activity.

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.