Analysis of polyaniline oligomers by laser desorption ionization and solventless MALDI.

While direct laser desorption ionization of soluble polyaniline dried onto metal sample plates results in mass spectra that are similar to previously shown electrospray ionization data of similar samples, laser desorption of unsolubilized solid polyaniline results in major fragmentation of the phenyl rings. Solventless MALDI, a recently developed technique for insoluble or slightly soluble species, involves the use of only solid analyte and matrix during sample preparation. Solventless MALDI of solid polyaniline results in mass spectra that are similar to the direct laser desorption ionization spectra of the soluble oligomers with some larger molecular weight oligomers also being detected. Based on the matrix used, different series of polyaniline with dissimilar end groups are detected. The matrix also affects the percentages of benzenoid and quinoid units in the oligomers. Thus, solventless MALDI appears to be a promising new technique for the mass spectrometric analysis of low solubility, but industrially important, polyanilines.