Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids : Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Blagojevic, V., Samad, S.N., Banu, L., Thomas, M.C., Blanksby, S.J., & Bohme, D.K. (2011) Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids : Ag2H+ and Cu2H+ ion formation in the presence of a double bond. International Journal of Mass Spectrometry, 299(2-3), pp. 125-130.

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Abstract

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and a-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also. Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly. Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion Ag-2(L-H)(+) where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I) (C).

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ID Code: 70652
Item Type: Journal Article
Refereed: Yes
Additional Information: Blagojevic, Voislav Samad, Sopeia N. Banu, Laura Thomas, Michael C. Blanksby, Stephen J. Bohme, Diethard K.
National Research Council (Canada); Natural Science and Engineering Research Council (Canada); MDS SCIEX; Australian Research Council [DP0986628]
DKB acknowledges continued financial support from the National Research Council (Canada), the Natural Science and Engineering Research Council (Canada) and MDS SCIEX. As holder of a Canada Research Chair in Physical Chemistry, DKB also thanks the contributions of the Canada Research Chair Program to this research. SJB acknowledges funding from the Australian Research Council (DP0986628).
Elsevier science bv
Amsterdam
Keywords: Metal cation complexes, Double bonds, Fatty acids, Lipids, Mass, spectrometry, electrospray-ionization, collisional activation, charge-remote, fragmentation, position, phospholipids, elucidation, location, leptin
DOI: 10.1016/j.ijms.2010.09.031
ISSN: 1387-3806
Divisions: Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 29 Apr 2014 03:17
Last Modified: 16 May 2014 06:26

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