Stereoisomeric Analysis of 6,10,14-Trimethylpentadecan-2-ol and the Corresponding Ketone in Wing Extracts from African Bicyclus Butterfly Species
Gas chromatography (GC) and mass spectrometry (MS) were used to determine the stereoisomeric compositions of 6,10,14-trimethylpentadecan-2-ol and 6,10,14-trimethylpentadecan-2-one in wing extracts from 17 Bicyclus butterfly species from different regions of Africa. All samples were purified using solid phase extraction (SPE). Since some species contained both alcohol and ketone, these were separated and the ketone was reduced to the alcohol before analysis as either (R)-trans-chrysanthemoyl or (S)-2-acetoxypropionyl esters. A novel asymmetric synthesis was developed for a reference mixture of (2R/S,6S,10R)-6,10,14-trimethylpentadecan-2-ol with known composition of the eight stereoisomers. The mixture then was used as the (R)-trans-chrysanthemoyl esters to correlate each of the eight gas chromatographic peaks to a specific stereoisomer of the extracted wing compounds. Seven butterfly species showed (2R,6R,10R)-configuration of the alcohol, four species contained minute amounts of alcohol too small to determine the stereochemistry, nine species showed (6R,10R)-configuration of the ketone, and one species contained minute amounts of ketone too small to determine the stereochemistry. No other stereoisomers of alcohol or ketone could be detected in the extracts, and the quantities of the compounds in the wing extracts varied from 5 to 900 ng per sample for each species.
Total synthesis of (+)-lactacystin.
A double stereodifferentiating crotylation between aldehyde 1 and silane (S)-2 to afford homoallylic alcohol 3 is the key diastereoselective step (anti:syn >30:1) in an efficient asymmetric synthesis of (+)-lactacystin. This compound is a metabolite isolated from Streptomyces sp. OM-6519 that exhibits significant neurotrophic activity. An additional important step in the synthesis is a catalytic asymmetric aminohydroxylation used as the key step in the synthesis of the (2R,3S)-hydroxyleucine synthon.
Energy skin effect of propellant particles in Electrothermal-Chemical Launcher
A numerical model of the radiation has been employed by a Monte Carlo method and statistical physics to simulate the process of a capillary plasma source for Electrothermal-Chemical (ETC) Launcher. The effect on propellants with different physical parameters is discussed. The plasma-propellant interaction is also discussed when combined with a thermal model. Results show that radiant energy only causes a small field around the plasma injector in the propellant bed. The responses of energy flux and propellant particles on radiation are both in the order of picosecond. The strong instantaneous radiation is responsible for the transmission of energy to the propellant particles leading to ignition. Compared with conventional ignition, the energy absorbed by propellant particles is used to increase quickly the temperature in the surface layer of propellant particles. This energy skin effect in the propellant particle surface appears to be the main cause of plasma ignition.