Charge transfer dissociation of phosphocholines: gas-phase ion/ion reactions between helium cations and phospholipid cations.

Phospholipid cations formed by electrospray ionization were subjected to excitation and fragmentation by a beam of 6 keV helium cations in a process termed charge transfer dissociation (CTD). The resulting fragmentation pattern in CTD is different from that of conventional collision-induced dissociation, but analogous to that of metastable atom-activated dissociation and electron-induced dissociation. Like collision-induced dissociation, CTD yields product ions indicative of acyl chain lengths and degrees of unsaturation in the fatty acyl moieties but also provides additional structural diagnostic information, such as double bond position. Although CTD has not been tested on a larger lipid sample pool, the extent of structural information obtained demonstrates that CTD is a useful tool for lipid structure characterization, and a potentially useful tool in future lipidomics workflows. CTD is relatively unique in that it can produce a relatively strong series of 2+ product ions with enhanced abundance at the double bond position. The generally low signal-to-noise ratios and spectral complexity of CTD make it less appealing than OzID or other radical-induced methods for the lipids studies here, but improvements in CTD efficiency could make CTD more appealing in the future.