Is there a 'matrix suppression effect' under fast-atom bombardment liquid secondary ion mass spectrometry of ionic surfactants in glycerol?

Some features of a 'matrix suppression effect' caused by ionic surface-active compounds under fast-atom bombardment (FAB) liquid secondary ion mass spectrometry (LSIMS) are being revised. It is shown that abundant transfer of the glycerol matrix molecules to the gas phase does occur under FAB-LSIMS of ionic surfactants, contrary to popular belief. This process can be obscure because of the dependence of the charge state of the glycerol-containing cluster ions on the type of ionic surfactant. It is revealed that, while glycerol matrix signals are really completely suppressed in the positive ion mass spectra of cationic surfactants (decamethoxinum, aethonium), abundant deprotonated glycerol and glycerol-anion clusters are recorded in the negative ion mode. In the case of an anionic surfactant (sodium dodecyl sulfate), on the contrary, glycerol is completely suppressed in the negative ion mode, but is present in the protonated and cationized forms in the positive ion mass spectra. It is suggested that such patterns of positive and negative ion FAB-LSIMS spectra of ionic surfactants solutions reflect the structure and composition of the electric double layer formed at the vacuum-liquid interface by organic cations or anions and their counterions. Processes leading to the formation of the glycerol-containing ions preferentially of positive or negative charge are discussed. The most obvious of them is efficient binding of glycerol to inorganic counterions of the salts Cl- or Na+, which is confirmed by data from quantum chemical calculations. The high content of the counterions and relatively small content of glycerol in the sputtered zone may be responsible for the charge-selective suppression of neat glycerol clusters of opposite charge to the counterions. In the case of a mixture of cationic and anionic surfactants the substitution of inorganic counterions by organic ones was observed. The dependence of the exchange rate in the surface layer is not a linear function of the bulk solution concentration, and an effect of abrupt recharging of the surface can be registered. No both positively or negatively charged pure glycerol and glycerol-inorganic counterion clusters are recorded for the mixture. Correlations between the mass spectrometric observations and some phenomena of surface and colloid chemistry and physics are discussed. Copyright (c) 2007 John Wiley & Sons, Ltd.