A method is described to obtain multicollision dissociation threshold (MCDT) values. These values provide relative reaction thresholds for dissociation in the three major gas-phase fragmentation reactions of oligosaccharides complexed to alkali metal ions. The quasimolecular ions are produced using matrix-assisted laser desorption/ionization Fourier transform mass spectrometry. The MCDTs for alkali metal ion dissociation and glycosidic bond and cross-ring cleavages were resolved from the kinetic energy dependence of collision-induced dissociation (CID) products. The relative strengths of alkali metal ion binding to N,N'-diacetylchitobiose (chitobiose) and N,N',N"-triacetylchitotriose (chitotriose) were probed using sustained off-resonance irradiation (SORI) CID. Experiments to evaluate MCDT values and the method for obtaining them were performed by studying alkali metal ion coordinated crown ethers. Molecular dynamic simulations were also performed to provide insight into the alkali metal ion binding of chitin-based oligosaccharides. The relative dissociation thresholds of glycosidic bond cleavages and cross-ring cleavages were determined for various alkali metal ion coordinated oligosaccharides. The activation barriers of glycosidic bond cleavages were found to depend on the size of the alkali metal ion. Cross-ring cleavages were found to be independent of the alkali metal ion but dependent on linkage type. The results suggest that glycosidic bond cleavages are charge-induced while cross-ring cleavages are charge-remote processes.

A new anion dopant for oligosaccharides is developed for use in matrix-assisted laser desorption/ionization mass spectrometry. Two types of sulfate-attached quasimolecular ions are formed in the negative ion mode when neutral oligosaccharides are doped with dilute H2SO4 solutions. Under mild conditions, i.e., low H2SO4 concentration (approximately 10(-3) M) and threshold laser fluence, a sulfate adduct [M + HSO4]- is formed. With more concentrated H2SO4 solutions (approximately 10(-2) M) and higher laser fluence, in situ derivatization of the oligosaccharides occurs to produce an ion whose m/z corresponds to a sulfate derivative [M + HSO4 - H2O]-. Hydrogen sulfate appears to be a general anion dopant because it forms complexes with a wide variety of neutral oligosaccharides. Conversely, anionic oligosaccharides form neither the adduct nor the derivative. The combination of complex formation (with neutral oligosaccharides) and the deprotonation of acidic oligosaccharides allows simultaneous detection of the respective mixture.

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Novel Dodecaarylporphyrins: Synthesis and Dynamic Properties -[preparation of 8 derivatives of type (I); NMR reveals several dynamic processes including a first example of β-aryl rotation]. -(MUZZI, CINZIA M.; MEDFORTH, CRAIG J.; VOSS, LISA; CANCILLA, MARK; LEBRILLA, CARLITO; MA, JIAN-GUO; SHELNUTT, JOHN A.; SMITH, KEVIN M.; Tetrahedron Lett. 40 (1999) 34, 6159-6162; Dep. Chem., Univ. Calif., Davis, CA 95616, USA; EN)