Tandem mass spectrometry of poly(methacrylic acid) oligomers produced by negative mode electrospray ionization View Full Text


Ontology type: schema:ScholarlyArticle      Open Access: True


Article Info

DATE

2009-01

AUTHORS

Rémi Giordanengo, Stéphane Viel, Béatrice Allard-Breton, André Thévand, Laurence Charles

ABSTRACT

Dissociation of small poly(methyl acrylic acid) (PMAA) anions produced by electrospray was characterized by tandem mass spectrometry. Upon collisional activation, singly, and doubly deprotonated PMAA oligomers were shown to fragment via two major reactions, dehydration and decarboxylation. The elimination of a water molecule would occur between two consecutive acid groups in a charged-remote mechanism, giving rise to cyclic anhydrides, and was shown to proceed as many times as pairs of neutral pendant groups were available. As a result, the number of dehydration steps, together with the abundance of the fragment ions produced after the release of all water molecules, revealed the polymerization degree of the molecule in the particular case of doubly charged oligomers. For singly deprotonated molecules, the exact number of MAA units could be reached from the number of carbon dioxide molecules successively eliminated from the fully dehydrated precursor ions. In contrast to dehydration, decarboxylation reactions would proceed via a charge-induced mechanism. The proposed dissociation mechanisms are consistent with results commonly reported in thermal degradation studies of poly(acrylic acid) resins and were supported by accurate mass measurements. These fragmentation rules were successfully applied to characterize a polymeric impurity detected in the tested PMAA sample. More... »

PAGES

25-33

Identifiers

URI

http://scigraph.springernature.com/pub.10.1016/j.jasms.2008.09.019

DOI

http://dx.doi.org/10.1016/j.jasms.2008.09.019

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1042437680

PUBMED

https://www.ncbi.nlm.nih.gov/pubmed/18926720


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