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Mixtures of methylated beta-cyclodextrins were characterized using three different methods of mass spectrometry: ionspray, atmospheric pressure chemical ionization (APCI) and matrix-assisted laser desorption/ionization (MALDI). Each of these methods allows a fast and simple determination of the degree of substitution, and can provide evidence for differences in the methylation of batches which have very similar global degrees of substitution. The three methods are in good qualitative agreement, but there are systematic differences in the quantitative results for the percentages of the various methylated molecules present in a batch. This is attributed to ionization yields which increase with the number of methyl groups, with different slopes for the different methods.

In matrix-assisted laser desorption/ionization mass spectrometry, carbohydrates ionize by attachment of an alkali cation, and the ion yield varies with the nature of the cation. In an attempt to contribute to the understanding of the mechanisms involved, we have conducted matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) experiments on the simple glucose molecule with the alkali cations Li+, Na+ and K+, and have also performed ab initio calculations. The calculations show that, for the most stable carbohydrate-cation geometry, the carbohydrate ring is twisted and the cation is coordinated to four oxygen atoms. Calculations also show that in these complexes the positions of the three cations are very similar, and the smaller the cation, the closer it is to the oxygen atoms. Finally, the calculated formation enthalpies of the different complexes agree with the experimental results obtained for the order of stability of these complexes.

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Emission of neutral and ionized Fe atoms induced by N2 laser irradiation (λ=337 nm) of iron targets was investigated for laser fluences ranging from the sputtering threshold (a few tens mJ/cm2) up to 320 mJ/cm2. The unique sensitivity of resonance ionization mass spectrometry permitted to identify the laser-sputtered neutral particles, to study their velocity distribution and excitation state, and to measure the laser-sputtering yield at a very low emission level (100 Fe atoms removed per laser shot). In this soft ablation mode, it appears that the sputtered atoms carry direct information on the primary mechanisms involved in the laser sputtering of an iron surface. The present study corroborates a thermal process in which the laser beam acts as a pulsed heat source. Energy characteristics of the emitted neutral atoms reflect rather well the thermal state of the surface, the atom temperature increasing from the ambient at threshold to melting and boiling temperatures for growing laser energies.

The mechanism of attachment of Na(+) on glucose, methyl-alpha-D-glucose, methyl-beta-D-glucose, 3-O-methylglucose, tetra-O-methylglucose, and also on galactose and methyl-beta-D-galactose, was studied. For this we measured the ion yields for the complex [sugar-Na(+)] formed by ionisation by matrix-assisted laser desorption/ionisation (MALDI) and ionspray. These data were compared with the relative volatilities and hydrophobicities of the sugars, measured by evaporative light scattering and reversed-phase liquid chromatography, respectively. Some formation enthalpies for the complexes [sugar-Na(+)], starting from the sugar and the cation, were obtained by ab initio calculations. No simple correlations could be observed between the ion yields and the parameters studied, so that the cationisation mechanism of the sugars remains unclear.

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