Protomers: formation, separation and characterization via travelling wave ion mobility mass spectrometry

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH3, whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO2 loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups. Copyright (C) 2012 John Wiley & Sons, Ltd.

Baccharis subgen. Molina (Asteraceae) no estado do Rio de Janeiro, Brasil

Baccharis compreende ca. 340 espécies distribuídas nas Américas. O indumento em tufos diminutos, formado por tricomas com uma única célula basal, e as flores funcionalmente unissexuais são caracteres diagnósticos do gênero. No estado do Rio de Janeiro ocorrem 55 espécies de Baccharis. O trabalho apresenta os resultados de estudos taxonômicos de Baccharis subgen. Molina (Pers.) Heering para a flora fluminense. No estado, o subgênero está representado por 18 espécies pertencentes a quatro seções - Caulopterae (8 spp.), Molinae (4 spp.), Baccharidastrum (3 spp.) e Trinervatae (3 spp.). É apresentada uma chave para a identificação das seções e espécies e descrições morfológicas, ilustrações, dados de distribuição geográfica e ecologia. Três espécies são novos registros e cinco são excluídas da lista de espécies do Rio de Janeiro.