title: A review of electron-capture and electron-transfer dissociation tandem mass spectrometry in polymer chemistry.
abstract: Mass spectrometry (MS)-based studies of synthetic polymers often characterise detected polymer components using mass data alone. However when mass-based characterisations are ambiguous, tandem MS (MS/MS) offers a means by which additional analytical information may be collected. This review provides a synopsis of two particularly promising methods of dissociating polymer ions during MS/MS: electron-capture and electron-transfer dissociation (ECD and ETD, respectively). The article opens with a summary of the basic characteristics and operating principles of ECD and ETD, and relates these techniques to other methods of dissociating gas-phase ions, such as collision-induced dissociation (CID). Insights into ECD- and ETD-based MS/MS, gained from studies into proteins and peptides, are then discussed in relation to polymer chemistry. Finally, ECD- and ETD-based studies into various classes of polymer are summarised; for each polymer class, ECD- and ETD-derived data are compared to CID-derived data. These discussions identify ECD and ETD as powerful means by which unique and diagnostically useful polymer ion fragmentation data may be generated, and techniques worthy of increased utilisation by the polymer chemistry community.
authors.affiliation: NSW Systems Biology Initiative, School of Biotechnology and Biomolecular Sciences, The University of New South Wales, Sydney, Australia. Electronic address: g.hart-smith@unsw.edu.au.
authors.forename: Gene
authors.initials: G
authors.lastname: Hart-Smith
mesh_terms: D002623:Chemistry Techniques, Analytical; D004579:Electron Transport; D004583:Electrons; D007477:Ions / Q000737:chemistry; D017785:Photons; D011108:Polymers / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D053719:Tandem Mass Spectrometry
chemical_list: D007477:Ions; D011108:Polymers
keywords: Collision-induced dissociation (CID); Electron-capture dissociation (ECD); Electron-transfer dissociation (ETD); Electrospray ionisation (ESI); Polymer chemistry; Tandem mass spectrometry (MS/MS)