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Abstract

The collision-induced dissociation (CID) spectra of the divalent metal complexes of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, [Metal^II(L)₂]²⁺ (where Metal = Cu²⁺, Mg²⁺ and Ca²⁺, L = [16:0/18:1GPCho]), formed by electrospray ionization, reveal interesting metal dependent fragmentation chemistry. Six main classes of reaction are observed corresponding to: two competing carboxylate abstraction pathways (from the sn1 and sn2 positions); phosphate abstraction; competing losses of the two different carboxylic acids from the sn1 and sn2 positions; loss of a protonated ligand, [L + H]⁺. The relative ratios of the competing carboxylate abstraction reactions are dependent on the metal, with the Cu and Ca complexes favoring the abstraction of the larger carboxylate (18:1) and the Mg complex favoring the abstraction of the smaller carboxylate (16:0).

Keywords

electrospray ionization tandem mass spectrometry collision induced dissociation diacylgycerophosphocholine

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References

Fisher

K.J.

, “Gas-phase coordination chemistry of transition metal ions”, Prog. Inorg. Chem. 50, 343 (2001). doi: 10.1002/0471227110.ch6

Teesch

L.M.

Adams

, “Metal-ions as Special Reagents in Analytical Mass Spectrometry”, Org. Mass Spectrom. 27, 931 (1992). doi: 10.1002/oms.1210270902

Allison

, “The Gas Phase Chemistry of Transition-Metal Ions in Analytical Mass Spectrometry”, Prog. Inorg. Chem. 34, 627 (1986).

James

P.F.

Perugini

M.A.

O'Hair

R.A.J.

, “Sources of artefacts in the electrospray ionization mass spectra of saturated diacylglycerophosphocholines: From condensed phase hydrolysis reactions through to gas phase intercluster reactions”, J. Am. Soc. Mass Spectrom. 17, 384 (2006). doi: 10.1016/j.jasms.2005.11.009

James

P.F.

Perugini

M.A.

O'Hair

R.A.J.

, “Size matters! Fragmentation chemistry of [Cu(L)_n]²⁺ complexes of diacylglycerophosphocholines as a function of coordination number (n = 2–7)”, Rapid Commun. Mass Spectrom. 21, 757 (2007). doi: 10.1002/rcm.2891

Hsu

F.F.

Turk

, “Electrospray ionization/tandem quadrupole mass spectrometric studies on phosphatidylcholines: The fragmentation processes”, J. Am. Soc. Mass Spectrom. 14, 352 (2003). doi: 10.1016/S1044-0305(03)00064-3

Cotton

F.A.

Wilkinson

, Advanced inorganic chemistry, 5th edition. John Wiley & Sons Inc., New York, USA, pp. 71–74 (1988).

Thomas

M.C.

Mitchell

T.W.

Blanksby

S.J.

, “Ozonolysis of phospholipid double bonds during electrospray ionization: A new tool for structure determination”, J. Am. Chem. Soc. 128, 58 (2006). doi: 10.1021/ja056797h

Letter: Collision-Induced Dissociation of [Metal(L) 2 ] 2+ Complexes (Metal = Cu,Ca and Mg) of 1-Palmitoyl-2-Oleoyl-sn-Glycero-3-Phosphocholine Allows Distinction of the Acyl Groups at the sn1 and sn2 Positions

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