CHARGE-REMOTE FRAGMENTATION DURING FAB-CAD-B/E LINKED-SCAN MASS-SPECTROMETRY OF AMINOETHYL-TRIPHENYLPHOSPHONIUM DERIVATIVES OF FATTY-ACIDS

The carboxyl group of fatty acids is derivatized by aminoethyl triphenylphosphonium (AETPP) bromide. Fast atom bombardment (FAB) collision-activated dissociation (CAD) B/E linked-scan mass spectrometry of these fixed-charge derivatives shows typical charge-remote fragmentation (CRF). Locations of various structural modifications in fatty acids can be recognized easily from CAD spectra of the AETPP derivatives. Because the triphenylphosphonium group localizes positive charge in the molecule, and because a key requirement for CRF is a tightly localized charge site, these preionized molecules fragment under FAB-CAD conditions more effectively than other derivatives that involve ionic bonding with metal cations or protonation of basic sites. Thus, CAD of AETPP derivatives is likely to produce more structurally informative spectra and provide an opportunity to gain additional understanding of the CRF process. The most profound difference between the AETPP derivatives and other cations in positive mode FAB-CAD-B/E-MS is reflected in the substantial improvement of detection limits for the AETPP derivatives over those for the metal cation adducts. For several fatty acids (C-10-C22) tested, the detectability can be enhanced by one to two orders of magnitude when the analysis is performed on the AETPP derivative. In addition, for the analysis of fatty acid mixtures, the FAB mass spectrum of AETPP derivatives produces a relative intensity of the molecular ion peak for each component of the mixture that more closely represents its mole fraction than does that of metal ion adducts.