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Amino Acids. 2016 Dec;48(12):2717-2729. Epub 2016 Aug 26.

Atypical cleavage of protonated N-fatty acyl amino acids derived from aspartic acid evidenced by sequential MS3 experiments.

Author information

1
IPCM UMR-CNRS 8232, University Paris VI (UPMC), Paris, France.
2
Université Oran 1 Ahmed Ben-Balla, Oran, Algeria.
3
MetaToul-Lipidomic, MetaboHUB, I2MC INSERM U1048, Toulouse, France.
4
CEA, iBiTec-S, SPI, LEMM, MetaboHUB, Gif Sur Yvette, France.
5
LCOMM Université de Mustafa Stambouli, Mascara, Algeria.
6
IPCM UMR-CNRS 8232, University Paris VI (UPMC), Paris, France. jean-claude.tabet@courriel.upmc.fr.
7
CEA, iBiTec-S, SPI, LEMM, MetaboHUB, Gif Sur Yvette, France. jean-claude.tabet@courriel.upmc.fr.

Abstract

Lipidomics calls for information on detected lipids and conjugates whose structural elucidation by mass spectrometry requires to rationalization of their gas phase dissociations toward collision-induced dissociation (CID) processes. This study focused on activated dissociations of two lipoamino acid (LAA) systems composed of N-palmitoyl acyl coupled with aspartic and glutamic acid mono ethyl esters (as LAA(*D) and LAA(*E)). Although in MS/MS, their CID spectra show similar trends, e.g., release of water and ethanol, the [(LAA(*D/*E)+H)-C2H5OH]+ product ions dissociate via distinct pathways in sequential MS3 experiments. The formation of all the product ions is rationalized by charge-promoted cleavages often involving stepwise processes with ion isomerization into ion-dipole prior to dissociation. The latter explains the maleic anhydride or ketene neutral losses from N-palmitoyl acyl aspartate and glutamate anhydride fragment ions, respectively. Consequently, protonated palmitoyl acid amide is generated from LAA(*D), whereas LAA(*E) leads to the [*E+H-H2O]+ anhydride. The former releases ammonia to provide acylium, which gives the C n H(2n-1) and C n H(2n-3) carbenium series. This should offer structural information, e.g., to locate either unsaturation(s) or alkyl group branching present on the various fatty acyl moieties of lipo-aspartic acid in further studies based on MS n experiments.

KEYWORDS:

ESI/MS n; Ion–dipole; N-fatty-acyl amino-acid; Regioselectivity

PMID:
27565657
DOI:
10.1007/s00726-016-2286-0
[Indexed for MEDLINE]

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