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.
The collision induced dissociation (CID) spectra of the divalent metal complexes of 1-palmitoyl-2-oleoyl-sn- glycero-3-phosphocholine, [Metal(lI)(L)(2)](2+) (where metal = Cu(2+), Mg(2+) and Ca(2+), L = [16:0/18:1GPCho]), formed by electrospray ionization, reveal interesting metal dependant 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 dependant on the metal, with the Cu and Ca complexes favouring the abstraction of the larger carboxylate (18:1) and the Mg complex favoring the abstraction of the smaller carboxylate (16:0).
James
Patrick F
PF
Perugini
Matthew A
MA
O'Hair
Richard A J
RA
D002118:Calcium / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D008274:Magnesium / Q000737:chemistry*; D010713:Phosphatidylcholines / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
D010713:Phosphatidylcholines; D003300:Copper; D008274:Magnesium; D002118:Calcium; C028694:1-palmitoyl-2-oleoylphosphatidylcholine