RESUMEN
Hydrogen-bridged radical cations (HBRCs) are an intriguing subclass of ion-molecule complexes. They may act as key intermediates of remarkable stability in both association and dissociation reactions of heteroatom-containing molecular ions. The H-bridge of such an HBRC can promote isomerization of its ionic component by H-transfer. Proton-transport catalysis (PTC) is a prime example. Here, a neutral molecule promotes the smooth transformation of an ion into its H-shift isomer by consecutive proton-transfer reactions. A celebrated case is the water catalyzed isomerization of CH(3)OH(â¢+) into its more stable distonic isomer (â¢)CH(2)OH(2)(+). Other early studies of PTC also deal with catalyzing 1,2-H shifts in association reactions. This short review focuses on more recent combined experimental and computational studies of catalysis in HBRCs. Mechanisms involving both proton and H atom transfers have been proposed for a variety of systems of H-shift isomers. It has also become clear that PTC is not confined to bimolecular reactions. It also features in the unimolecular chemistry of heteroatom- containing ions, which have a tendency to isomerize to HBRCs en route to their dissociation.
RESUMEN
In matrix-assisted laser desorption/ionization (MALDI) analyses of small oligosaccharides a very large increase in sensitivity (by a factor of 1000) may be obtained by introducing a quaternary ammonium center ('quaternization'). Such a quaternary ammonium center may be introduced into the saccharide by reaction with commercially available glycidyltrimethylammonium chloride (GTMA), or by using Girard's reagent T (Naven and Harvey, Rapid Commun. Mass Spectrom. 1996; 10: 829). GTMA reacts with alcohol functionalities, whereas Girard's reagent T is specific for aldehyde and keto groups. Thus reducing saccharides can be derivatized by both GTMA and Girard's reagent T. For example, glucose or cellobiose having a stock concentration of 3 x 10(-5) M (5 microg/mL) produces no sugar-derived signals in conventional MALDI, but their quaternized derivatives, also at 3 x 10(-5) M, yield intense signals, with the matrix-derived signals only being weak. Similar results were obtained for glucosamine. Non-reducing saccharides as well as sugar alcohols can be derivatized using GTMA; thus, although sucrose, raffinose and sorbitol do not react with Girard's reagent T, they all produce intense signals after derivatization with GTMA. An example of the application of these derivatization reactions is provided by the analysis of oligosaccharides in beer.