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Characterization of acyl chain position in unsaturated phosphatidylcholines using differential mobility-mass spectrometry

Journal Article


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Abstract


  • Glycerophospholipids (GPs) that differ in the relative position of the two fatty acyl chains on the glycerol backbone (i.e., sn-positional isomers) can have distinct physicochemical properties. The unambiguous assignment of acyl chain position to an individual GP represents a significant analytical challenge. Here we describe a workflow where phosphatidylcholines (PCs) are subjected to ESI for characterization by a combination of differential mobility spectrometry and MS (DMS-MS). When infused as a mixture, ions formed from silver adduction of each phospholipid isomer {e.g., [PC (16:0/18:1) + Ag]+ and [PC (18:1/16:0) + Ag]+} are transmitted through the DMS device at discrete compensation voltages. Varying their relative amounts allows facile and unambiguous assignment of the sn-positions of the fatty acyl chains for each isomer. Integration of the well-resolved ion populations provides a rapid method (< 3 min) for relative quantification of these lipid isomers. The DMS-MS results show excellent agreement with established, but time-consuming, enzymatic approaches and also provide superior accuracy to methods that rely on MS alone. The advantages of this DMS-MS method in identification and quantification of GP isomer populations is demonstrated by direct analysis of complex biological extracts without any prior fractionation.

UOW Authors


  •   Maccarone, Alan (external author)
  •   Duldig, Jackson (external author)
  •   Mitchell, Todd
  •   Blanksby, Stephen J. (external author)
  •   Duchoslav, Eva (external author)
  •   Campbell, J Larry. (external author)

Publication Date


  • 2014

Citation


  • Maccarone, A. T., Duldig, J., Mitchell, T. W., Blanksby, S. J., Duchoslav, E. & Campbell, J. Larry. (2014). Characterization of acyl chain position in unsaturated phosphatidylcholines using differential mobility-mass spectrometry. Journal of Lipid Research, 55 (8), 1668-1677.

Scopus Eid


  • 2-s2.0-84905038107

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=3585&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/2566

Number Of Pages


  • 9

Start Page


  • 1668

End Page


  • 1677

Volume


  • 55

Issue


  • 8

Abstract


  • Glycerophospholipids (GPs) that differ in the relative position of the two fatty acyl chains on the glycerol backbone (i.e., sn-positional isomers) can have distinct physicochemical properties. The unambiguous assignment of acyl chain position to an individual GP represents a significant analytical challenge. Here we describe a workflow where phosphatidylcholines (PCs) are subjected to ESI for characterization by a combination of differential mobility spectrometry and MS (DMS-MS). When infused as a mixture, ions formed from silver adduction of each phospholipid isomer {e.g., [PC (16:0/18:1) + Ag]+ and [PC (18:1/16:0) + Ag]+} are transmitted through the DMS device at discrete compensation voltages. Varying their relative amounts allows facile and unambiguous assignment of the sn-positions of the fatty acyl chains for each isomer. Integration of the well-resolved ion populations provides a rapid method (< 3 min) for relative quantification of these lipid isomers. The DMS-MS results show excellent agreement with established, but time-consuming, enzymatic approaches and also provide superior accuracy to methods that rely on MS alone. The advantages of this DMS-MS method in identification and quantification of GP isomer populations is demonstrated by direct analysis of complex biological extracts without any prior fractionation.

UOW Authors


  •   Maccarone, Alan (external author)
  •   Duldig, Jackson (external author)
  •   Mitchell, Todd
  •   Blanksby, Stephen J. (external author)
  •   Duchoslav, Eva (external author)
  •   Campbell, J Larry. (external author)

Publication Date


  • 2014

Citation


  • Maccarone, A. T., Duldig, J., Mitchell, T. W., Blanksby, S. J., Duchoslav, E. & Campbell, J. Larry. (2014). Characterization of acyl chain position in unsaturated phosphatidylcholines using differential mobility-mass spectrometry. Journal of Lipid Research, 55 (8), 1668-1677.

Scopus Eid


  • 2-s2.0-84905038107

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=3585&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/2566

Number Of Pages


  • 9

Start Page


  • 1668

End Page


  • 1677

Volume


  • 55

Issue


  • 8