Fast Atom Bombardment Mass Spectrometry: Matrix Effects on Ion Formation and Fragmentation
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Matrix effects on the competitive formation and extents of fragmentation of M+· and [M+H]+ ions produced under fast atom bombardment (FAB) conditions, and on the formation of complex [M+matrix+H]+ and [M+matrix-H]- ions under FAB conditions have been described using various organic compounds. The use of hydrophilic matrices such as glycerol and thioglycerol resulted in the preferential formation of [M+H]+ to M+· ions compared to the use of hydrophobic matrices such as m-nitrobenzyl alcohol and o-nitrophenyloctyl ether. The use of alcoholic-hydrophilic matrices such as glycerol and pentamethylene glycol resulted in the preferential formation of [M+H]+ to M+· ions compared to the use of thiol-containing hydrophilic matrices such as thioglycerol and dithiothreitol. The latter matrix effect was explained on the basis of the distinction of hydrogenbonding ability between hydroxyl -OH and thiol -SH groups, and it was proposed that the hydrogen-bonding interaction between the hydroxyl group(s) of matrix and the basic site(s) of analyte molecules in matrix solution, which was named as a ‘quasi-preformed state’, is advantageous for the formation of [M+H]+ to M+· ions. It was confirmed that the fragmentation of [M+H]+ and M+· ions produced under FAB conditions occurs independently to each other and that the extent of fragmentation of M+· ions is often comparable to that of fragmentation of M+· ions formed at 70 eV or above in the electron impact ionization method. The extent of fragmentation of M+· ions under FAB conditions depended upon the matrix materials used. Further, the extent of fragmentation of [M+H]+ ions under FAB conditions was larger than that of fragmentation of [M+H]+ ions formed by the isobutane chemical ionization method. The complex ions, [M+matrix+H]+ and [M+matrix-H]-, were formed by the use of a certain prenylated flavone and thiol-containing matrices, while the complex ions were not formed by the use of the flavone lacking a prenyl group or glycerol matrix. The suitability of matrix materials for positive- and negative- ion FAB mass spectrometry has been discussed.
- 日本質量分析学会の論文
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