Fluorinated matrix approach for the characterization of hydrophobic perfluoropolyethers by matrix-assisted laser desorption/ionization time-of-flight MS

Characterization of fluorinated polymers in MALDI is often unsuccessful because commonly used matrixes, such as 2,5-dihydroxybenzoic acid, Indole acrylic acid, alpha-cyano-4-hydroxycinnamic acid, etc., do not desorb/ionize fluorinated polymers efficiently. This could be in part attributed to the unfavorable interaction between the matrix molecules and fluorinated oligomers due to differences in their hydrophobicities. Moreover, the relative cation affinity between the matrix molecules and the fluorinated oligomers may not favor the gas-phase cationization process of the fluorinated oligomers. To overcome these limitations, fluorinated derivates of benzoic acid (pentafluorobenzoic acid) and cinnamic acid (Pentafluoro cinnamic acid) were employed for the desorption/ionization of perfluoropolyethers. Presence of fluorine atoms in the matrix might improve the interaction between the matrix and perfluoroether during the crystallization or ionization step. With a pentafluorobenzoic acid matrix, intact silver cationized oligomers were desorbed, whereas with a pentafluorocinnamic acid matrix, loss of end group was observed. This loss could be rationalized by the dissociation of the silver cationized oligomers via an ion-dipole mechanism. This work shows the possibility of characterizing yet another important class of fluorinated polymer by MALDI-TOFMS.