How feasible is matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry analysis of polyolefins?

Ab initio quantum calculations were applied to obtain binding energies for sodium cation-oligomer complexes comprising either methanol, ethylene glycol oligomers or n-alkanes. In addition, it was experimentally shown using sodium cations that ethylene glycol oligomers could not be detected when consisting of less than 5 monomers. This observation and the fact that experimentally no matrix-assisted laser desorption/ionisation mass spectra have been reported for saturated polyolefins are now attributed to the low binding energy of the sodium-oligomer complexes, which is insufficient to prevent dissociation of the complexes in multiple collisions occurring in the extraction section of the mass spectrometer. (C) 1998 John Wiley & Sons, Ltd.