A method for the quantitation of diesterditerpene-type Aconitum alkaloids and their hydrolysis products by gas chromatography-selected ion monitoring was applied to a clinical case study. A 45-year-old male attempted suicide by oral intake of Aconitum alkaloids, which are highly intoxicant extracts of Aconitum tubers. It was estimated that he had ingested approximately 11 mg of diesterditerpene-type alkaloids but was saved by intensive gastric irrigation. Mesaconitine, aconitine, hypaconitine, and their hydrolysis products were detected in the serum on the first day only. On the other hand, some alkaloids were still detectable in the urine even six days after intoxication. Aconitum alkaloids are biotransformed, and their hydrolysis products are excreted time-dependently to the urine. The urine was a useful material to identify the toxicants in the case of aconite intoxication.

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This paper describes a newly developed method using gas chromatography-selected ion monitoring (GC-SIM) for the simultaneous determination of diester-diterpene type Aconitum alkaloids and their hydrolysis products in human serum. When the alkaloids were converted into their TMS derivatives, they produced a well defined peak on selected ion recording (SIR). Good linear response over the range of 100 pg to 7.5 ng was demonstrated for each alkaloid. When the alkaloids were spiked into human serum, good quantitative recovery was observed.

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A rapid, specific and precise method using GC/SIM was applied to separate and quantify Aconitum alkaloids in Aconitum tubers. The TMS derivatives of each alkaloid produced a well defined peak on selected ion recording (SIR). Good linear response over the range of 100 pg - 7.5 ng was demonstrated for each alkaloid. Furthermore, we investigated the changes in the contents of Aconitum alkaloids, i.e., hypaconitine, mesaconitine, aconitine, and jesaconitine, in Aconitum tubers paying special attention to the harvesting season. Mesaconitine had the highest value in all seasons. Mesaconitine and aconitine showed the highest value in the samples harvested in May 1991 while hypaconitine had the highest value among those harvested in December 1990. As to the total amount of the alkaloids, the highest value, 4190 microg/g, and the lowest value, 1881 microg/g, were observed in the samples harvested in May and September, respectively. GC/SIM was very useful for the determination of Aconitum alkaloids in the tubers.