Premium
The sequential dissociation of protonated polyethylene glycols
Author(s) -
Hester Thomas H.,
McCraney Kendra K.,
Castillo Daniel E.,
Goebbert Daniel J.
Publication year - 2013
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.3177
Subject(s) - chemistry , dissociation (chemistry) , protonation , fragmentation (computing) , monomer , acetaldehyde , polyethylene glycol , collision induced dissociation , ion , hydride , photochemistry , computational chemistry , mass spectrometry , organic chemistry , ethanol , chromatography , tandem mass spectrometry , polymer , hydrogen , computer science , operating system
Early investigations of protonated polyethylene glycol fragmentation suggested the dissociation mechanism includes both direct and sequential processes. Experiments designed to study the proposed mechanisms of sequential dissociation are absent from the literature. In order to obtain additional experimental details about the fragmentation reactions, the dissociation of protonated polyethylene glycol was studied by energy‐dependent collision‐induced dissociation (CID). Key fragment ions were separated by mass differences corresponding to the loss of single monomer units. Several fragment ions were also generated by in‐source fragmentation and studied by CID. These experiments indicate the primary ions undergo sequential dissociation by the loss of either one or two monomer units. The results suggest that at least two different mechanisms must be considered to explain the sequential dissociation of protonated polyethylene glycols. The reaction involving the elimination of two subunits suggests the loss of a six‐membered 1,4‐dioxane product, while the elimination of a single subunit involves the loss of acetaldehyde by a 1,2‐hydride shift rearrangement. Copyright © 2013 John Wiley & Sons, Ltd.