Charge-remote fragmentation of lithiated fatty acids on a TOF-TOF instrument using matrix-ionization.
In numerous studies charge remote fragmentation (CRF) has been shown to be a powerful technique for determination of primary structure by allowing location of double bonds, various functional groups, and branching in a variety of compound types directly by mass spectrometry. Instrumentation and ionization methods traditionally used for CRF, however, are becoming rare, in large part because ESI and MALDI have to a significant extent replaced them. Here we demonstrate that by selecting a matrix that promotes rather than suppresses ionization of fatty acids (FA) by lithium ion adduction, and using a TOF-TOF mass spectrometer for high-energy collisional activation, CRF ions are produced that allow location of double-bond and branching positions. Further, we show that by using solvent-free MALDI sample preparation methods, thus eliminating the inherent segregation of the hydrophobic fatty acid from the hydrophilic LiCl that can occur during the evaporation of solvent, the desired [FA-H+2Li](+) ions are greatly enhanced. Because FAs can be vaporized using laser desorption, matrix assistance in desorption of the fatty acid may occur, but is not necessary. However, the matrix plays a crucial role in enhancing or suppressing ionization. For example, matrix materials with acid (e.g., 2,5-dihydroxybenzoic acid) or hydroxy groups (e.g., dithranol) compete with the FA for Li(+) and because of the high ratio of matrix to analyte, FA lithium adduction is minimized. However, highly electron-deficient matrix materials (e.g., TCNQ) readily donate Li(+) to FAs because of the instability associated with being positively charged.
Trimpin
Sarah
S
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA. strimpin@indiana.edu
Clemmer
David E
DE
McEwen
Charles N
CN
D005227:Fatty Acids / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*
D005227:Fatty Acids; D008094:Lithium