Abstract
Desorption chemical ionization mass spectrometry (DVI-MS) was investigated as a technique for obtaining the structural characterization of perfluorinated polyethers (PFPE). Negative-ion DCI mass spectra were dominated by sequences of oligomeric alkoxy fragment ions, each retaining one of the polymeric chain. Ion abundances showed Gaussian distributions, which were ascribed to low-energy deposition during desorption. The most important process in the gas-phase ion chemistry of PFPEs resulted in the cleavage of C-O bonds, associated with charge retention on the oxygen; only low-intensity peaks were due to formation of carbanions
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