Localization of fatty acyl and double bond positions in phosphatidylcholines using a dual stage CID fragmentation coupled with ion mobility mass spectrometry

Jose Castro-Perez, Thomas P. Roddy, Nico M.M. Nibbering, Vinit Shah, David G. McLaren, Stephen Previs, Athula B. Attygalle, Kithsiri Herath, Zhu Chen, Sheng Ping Wang, Lyndon Mitnaul, Brian K. Hubbard, Rob J. Vreeken, Douglas G. Johns, Thomas Hankemeier

Research output: Contribution to journalArticlepeer-review

102 Scopus citations

Abstract

A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M + Li] + was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C15H31CO +, m/z 239) or 18:1 (9Z) (C17H33CO+, m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H2C-HC = CH-CH = CH2). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of 13C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC.

Original languageEnglish
Pages (from-to)1552-1567
Number of pages16
JournalJournal of the American Society for Mass Spectrometry
Volume22
Issue number9
DOIs
StatePublished - Sep 2011

Keywords

  • CID fragmentation
  • Double bond position
  • Fatty acids
  • Ion mobility
  • Mass spectrometry
  • Phosholipids
  • Time-of-flight

Fingerprint

Dive into the research topics of 'Localization of fatty acyl and double bond positions in phosphatidylcholines using a dual stage CID fragmentation coupled with ion mobility mass spectrometry'. Together they form a unique fingerprint.

Cite this