Structural analysis of choline phospholipids by fast atom bombardment mass spectrometry and tandem mass spectrometry.
The structures of intact choline phospholipids were determined by positive and negative ion mode fast atom bombardment mass spectrometry, tandem mass spectrometry, and B2/E and B/E constant linked scan mass spectrometry. The molecular weight of the choline lipid could be clearly determined by the appearance of [M + H]+ or [M + Na]+ in the positive ion mode and triplet ions, e.g., [M - 15]-, [M - 60]-, and [M - 86]-, in the negative ion mode. The structures of the triplet ions were assigned to [M - CH3]-, [M - HN(CH3)3]-, and [M - CH2 = CHN(CH3)3]-, respectively, by the MS/MS of each triplet ion, and the origin of the triplet ions was found as the matrix-ion adduct to the target molecule by using the B2/E linked scan technique. The polar group could be identified by the existence of ions indicating glycerophosphocholine and its cleavage products and by the presence of the triplet ions in the negative ion mode. Positional determination of the distribution of constituent fatty acyl groups was carried out by comparing the intensity of deacylated ions from positions 1 and 2 in the positive ion mode and of the ions produced by MS/MS of the triplet ions. From the mass number of the [RCOO]- ion which appeared in the negative ion mode, the molecular weight and degree of unsaturation of the fatty acyl group were determined. The position of double bond(s) in the acyl group was determined from the MS/MS of the [RCOO]- ion.
Hayashi
A
A
Department of Chemistry, Faculty of Science and Technology, Kinki University, Osaka.
Matsubara
T
T
Morita
M
M
Kinoshita
T
T
Nakamura
T
T
D008244:Lysophosphatidylcholines / Q000032:analysis; D013058:Mass Spectrometry; D010713:Phosphatidylcholines / Q000032:analysis*; D013109:Sphingomyelins / Q000032:analysis
D008244:Lysophosphatidylcholines; D010713:Phosphatidylcholines; D013109:Sphingomyelins