Enantiomeric purity deviations of radiolabelled amino acids obtained from chiral columns

Enantiomeric purity (EP) is an important value which denotes the relative percentage of the L-isomer with respect to the D-isomer. For 11C and 18F-labelled amino acid (AA) radiopharmaceutical (RP) production, EP represents a quality control parameter specified in European and national monographs for particular RPs. In most instances, EP value of greater then 90 or 95% (depending on AA type) is required as part of the quality control (QC) value of a RP following radiosynthesis. In common practice, two chromatographic columns are used for the EP determination of RPs: Crownpak CR(+) (Daicel), which contains a crown ether stationary phase or Chirobiotic T (Astec), which contains silica-bound glycoproteins as the stationary phase. The application of column Crownpak CR(+) requires that only perchloric acid solution (with pH 1–2) may be used, as the retention capability of the stationary phase is greatly reduced using organic solvents. This work intends to identify which chromatographic system is more accurate and reliable for EP determination as part of QC. We performed a series of parallel injections of the same batch of the widely used AA RPs [11C]MET and [18F]FET on the two aforementioned columns. The EP determination using column Crownpak CR(+) consistently provided a lower EP value compared to the Chirobiotic T column; the EP deviation between the respective columns was found to range from 2.4–4.0% for the same RP sample. Furthermore, the EP value was influenced by a sample’s dilution factor, e.g. the EP was observed to increase up to 1.5% when the radioactive sample had a fivefold dilution factor. This phenomenon was consistent for both Crownpak CR(+) and Chirobiotic T columns. Finally, a series of standard solutions of non-radioactive methionine with various ratios of L-and D-isomers was analyzed. The data obtained for non-radioactive methionine confirmed that column Crownpak CR(+) incorrectly provided a higher D-enantiomer concentration, whereas Chirobiotic T was found to provide a lower D-enantiomer concentration of the same sample. The deviation from the theoretical EP value was between 0.67 and 1.92%.

Sexual cannibalism increases male material investment in offspring: quantifying terminal reproductive effort in a praying mantis

Models of the evolution of sexual cannibalism argue that males may offset the cost of cannibalism if components of the male body are directly allocated to the eggs that they fertilize. We tested this idea in the praying mantid Tenodera sinensis . Males and females were fed differently radiolabelled crickets and allowed to mate. Half of the pairs progressed to sexual cannibalism and we prevented cannibalism in the other half. We assess the relative allocation of both male-derived somatic materials and ejaculate materials into the eggs and soma of the female. Our results show that male somatic investment contributes to production of offspring. The eggs and reproductive tissues of cannibalistic females contained significantly more male-derived amino acids than those of non-cannibalistic females, and there was an increase in the number of eggs produced subsequent to sexual cannibalism. Sexual cannibalism thus increases male material investment in offspring. We also show that males provide substantial investment via the ejaculate, with males passing about 25% of their radiolabelled amino acids to females via the ejaculate even in the absence of cannibalism.