Tandem mass spectrometric approach for determining structure of molecular species of aminophospholipids

Aminophospholipids, including glycerophosphatidylethanolamine, glycerophosphatidylserine and their Lyso analogous, have been analyzed by positive and negative ion liquid secondary ion ionization coupled to tandem mass spectrometry. The mass spectra of aminophospholipids obtained by tandem mass spectrometers with different configuration (liquid secondary ion-electric-magnetic sector coupled to quadrupole mass analyzer (low-energy collision) or electric-magnetic sector (high-energy collision), as well as electrospray ionization-quadrupole mass analyzer combined with quadrupole mass analyzer (low-energy collision), are compared. The mass spectra produced by low-energy collisionally induced dissociation of the deprotonated molecules from aminophospholipids contain fragment ions for characterizing polar head moieties as well as fatty acid composition and position. The mass spectra generated by high-energy collisionally induced dissociation of both protonated and deprotonated molecules from aminophospholipids show numerous product ions for identifying polar heads, composition, and location of fatty acid chains in molecular species. Triple quadrupole mass spectrometer with electrospray ionization exhibits remarkable superiority in detection sensitivity. Liquid secondary ion with electric-magnetic sector coupled to quadrupole mass analyzer or electric-magnetic sector instrument has the advantage of the capability of properly determining location of fatty acid chains in molecular species. This paper also describes an approach for structurally analyzing aminophospholipid species as 9-fluorenylmethyloxycarbonyl derivatives by positive and negative ion liquid secondary ion mass spectrometry and high-energy collisionally induced dissociation tandem mass spectrometry. It has been found that the derivatives of glycerophosphatidylethanolamine and glycerophosphatidylserine can readily be analyzed by the negative ion liquid secondary ion and tandem mass spectrometric methods.