The clinical presentation of patients with hourglass-like constrictions in their nerves is similar to that of patients with neuralgic amyotrophy. Histochemical analysis suggests that the pathogenesis may be immunological in origin. The role of surgery in this condition is uncertain.
Five new stilbene oligomers, laetevirenol A-E (4-8), were isolated from Parthenocissus laetevirens, together with three known stilbene oligomers (2, 3, and 9). The structures of the new compounds were elucidated by spectroscopic analysis, including 1D and 2D NMR experiments. Afterward the absolute configurations were determined. Biomimetic transformations revealed a possible biogenetic route, where stilbene trimers were enzymatically synthesized for the first time. In addition, their antioxidant activities were evaluated by 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. The results showed that stilbene oligomers with an unusual phenanthrene moiety exhibited much stronger antioxidant activities. Thus, the photocatalyzed cyclization of stilbenes was supposed to be an antioxidant activity promoting transformation, which was hypothesized to play a role in the antioxidative defense system of the plant.
The fragmentation of protonated molecules (MH(+)) in mass spectrometry usually results in even-electron product ions, but the MH(+) ions of sulfonamides are different as they often produce dominant radical cations of the constituent amines. For a series of benzenesulfonamides of anilines that bear various substituents, we found that the sulfonamides are preferentially protonated at the nitrogen, which is different from the carboxylic amides. Upon N-protonation, the S-N bond dissociates spontaneously to produce an intermediate [sulfonyl cation/aniline] complex. Within the ion-neutral complex, charge transfer between the two partners occurs in the gas phase to give rise to the ionized anilines. A substantial energy barrier was found to govern the reaction, which is consistent with the outer-sphere electron transfer mechanism. This energy barrier prevents the charge transfer when a strong electron-withdrawing substituent is attached to the aniline moiety. In contrast, when the aniline bears an electron-donating group, charge transfer is still more favorable than the dissociation of the intermediate ion-neutral complex, in spite of the existence of the energy barrier, and therefore dominates. A correlation was observed between the intensities of the ionized anilines and the ionization energies of these anilines.
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