Cantharidin, a potent defensive chemical, is present in all ten life stages of the blister beetle Epicauta funebris. The first five larval stages accumulate cantharidin as they feed and grow in size. When disturbed, they exude cantharidin in a milky oral fluid, not in hemolymph which adult beetles reflexively discharge from leg joints. Two subsequent larval stages and the pupa do not feed, grow, regurgitate, or change in their defensive reserves (110 micrograms cantharidin/insect, regardless of sex). Adult beetles kept in isolation for 60-90 d exhibit a pronounced sexual dimorphism in cantharidin production: the male biosynthesizes about 17 mg of the toxin, representing 10% of his live weight, whereas the female actually loses most of her defensive reserves. But in the wild a female beetle repeatedly acquires cantharidin as copulatory gifts from her mates.
Several sampling methods were examined to determine their efficiency at recovering the cuticular hydrocarbons, including solvent washing, extraction, and dynamic headspace analysis. Hexane proved to be an acceptable solvent for obtaining a representative hydrocarbon sample, but is not a good solvent for quantitative recoveries, unless special measures are taken. This appears to be as a result of both limitations in solubility and kinetic problems. Dynamic headspace analysis using a pyroprobe for thermal desorption of the hydrocarbons proved to be a rapid and quantitative sampling method.
A highly selective, sensitive method for determination of carboxylic acids in water has been developed that is based on fluorine-selective gas chromatography (GC) detection of pentafluorobenzyl ester derivatives. The atmospheric-pressure helium microwave-induced plasma detector is well suited for fluorine-specific detection of these derivatives, which were well resolved by capillary GC and displayed a characteristic fragmentation behavior when examined by GC-mass selective detection. For demonstration purposes, a number of carboxylic acids, ranging from C1 to C20, were examined and found to be derivatized with yields greater than 90%, and a sample of creek water was examined for its carboxylic acid content.
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