Features of the splitting out of a methyl radical from lycoctonine alkaloids under electron impact
The mass spectra of 53 alkaloids and their derivatives are considered. It is known that the presence of a C6(OCH3)-C7(OH)-C8 (OH) grouping in C19-diterpene alkaloids leads to a high intensity of the (M - 15)+ ions at the expense of the C6(OCH3) group and considerably suppresses the competing processes of forming the [M - OH (OCH3)]+ ions in the alkaloids and the (M - 56)+ ions in the anhydroxy bases. When the above-mentioned grouping is absent, the (M - 15)+ ions are formed mainly by the splitting out of a ĊH3 from a N-ethyl group.
Fragmentation study of aminoalcohol-diterpenoid alkaloids by electrospray ionization time-of-flight mass spectrometry.
RATIONALE
Aminoalcohol-diterpenoid alkaloids were found to be a group of cardioactive substances in the lateral roots of Aconitum carmichaeli Debx. Studies on the fragmentation behaviors and features of these alkaloids in mass spectrometry would be important for their structural identification and in vivo metabolic research, which has not received much attention thus far.


METHODS
In this study, the fragmentation behaviors of 14 aminoalcohol-diterpenoid alkaloids were investigated by utilizing high-resolution time-of-flight tandem mass spectrometry. By analysis of the obtained MS(2) data, we summarized the fragmentation features of the corresponding alkaloids under different collision energy.


RESULTS
The dissociation of functional groups from the skeleton was observed as the main fragmentation way in electrospray ionization (ESI) mode. The order of fragmentation sites was C1/C3 > C16 > C15 > C6 > N, with loss of one or more CH3OH, H2O, C2H4 (substituent on N atom) or CO (at C15 ) groups.


CONCLUSIONS
The first systematic investigations on the fragmentation of aminoalcohol-diterpenoid alkaloids are described in this paper, setting the stage for an in-depth identification and study of the corresponding components in complex systems.
Philip Roth’s Great Books: A Reading of The Human Stain
Philip Roth belongs to the first generation of American novelists for whom a university education in the liberal arts was the norm. This essay charts Roth’s developing acquaintance with classical literature, the starting point for Great Books courses in the 1950s, and the implications for his fiction of his understanding of the difference in scope and purpose between the two representative classical genres. It focuses on The Human Stain (2000), the novel in which he reflects most directly upon what tragedy and epic once did, and what might happen to novels if they became more like the one or the other.