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PMID: 18258448 Published · ppublish English Evaluation Study Journal Article Research Support, Non-U.S. Gov't Research Support, U.S. Gov't, Non-P.H.S.

Desorption electrospray ionization (DESI) mass spectrometry and tandem mass spectrometry (MS/MS) of phospholipids and sphingolipids: ionization, adduct formation, and fragmentation.

Journal of the American Society for Mass Spectrometry ·Vol. 19 ·No. 4 ·2008-04-00 ·Pages 531-43

Manicke NE, Wiseman JM, Ifa DR, Cooks RG

Abstract

Desorption electrospray ionization (DESI) mass spectrometry was evaluated for the characterization of glycerophospholipid standards, including glycerophosphocholine (GPCho), glycerophosphoglycerol (GPGro), glycerophosphoethanolamine (GPEtn), glycerophosphoserine (GPSer), glycerophosphoinositol (GPIns), cardiolipin (CL), and sphingolipid standards, including sulfatides (ST) and sphingomyelin (SM). Of specific interest were the effects of surface and solvent composition on signal stability and intensity, along with the ions observed in the full scan mode and the fragmentations seen upon collisional activation for each of the above classes. These experiments were performed without the addition of matrix compounds to the sample and were conducted in the free ambient environment at atmospheric pressure. The compounds GPSer, GPGro, GPIns, ST, and CL were best analyzed in the negative ion mode while PE was ionized efficiently in both positive and negative ion modes. SM and GPCho, which typically generate more abundant ions in the positive ion mode, could be analyzed in the negative ion mode by the addition of anionic reagents such as acetate to the spray solvent. Full scan DESI mass spectra and tandem (MS/MS) spectra for this representative set of physiological phospho/sphingolipids are presented. Similarities with other ionization methods in terms of fragmentation behavior were strong, although ambient ionization of untreated samples is only available with DESI. The effect of surface and solvent properties on signal intensity and stability were determined by depositing standard compounds on several different surfaces and analyzing with various proportions of methanol in the aqueous spray. Analysis was extended to complex mixtures of phospholipids and sphingolipids by examining the total lipid extract of porcine brain and by direct analysis of rat brain cryotome sections. These types of mixture analyses and molecular imaging studies are likely to represent major areas of application of DESI.

MeSH Terms
Animals Brain Chemistry Glycerophospholipids/chemistry Rats Spectrometry, Mass, Electrospray Ionization/methods Sphingolipids/chemistry Swine Tandem Mass Spectrometry/methods
Chemicals
Glycerophospholipids Sphingolipids
Authors & Affiliations
4 authors, click to expand affiliations / ORCID
Manicke Nicholas E
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA.
Wiseman Justin M
Ifa Demian R
Cooks R Graham
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Article Info
Journal
Journal of the American Society for Mass Spectrometry
Abbr.
J Am Soc Mass Spectrom
ISSN
1044-0305
DOI
10.1016/j.jasms.2007.12.003
Published
2008-04-00
Epub
2007-00-27
Pages
531-43
Language
English
Region
United States
NLM ID
9010412
Subset
IM
External Links
PubMed source DOI: 10.1016/j.jasms.2007.12.003 View journal details
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