Tandem Fourier transform mass spectrometry of block and random copolymers

Electron transfer dissociation versus collisionally activated dissociation of cationized biodegradable polyesters

“…[34][35][36] Four polymer systems have so far been investigated by ECD, viz. poly(ethylene oxide-co-propylene oxide) and poly (methyl methacrylate-co-butyl methacrylate) copolymers, [37][38][39] polyesteramides [40] and poly(amidoamine) dendrimers. [41] ECD resulted in simpler and more informative spectra for the polyethers and dendrimers, but yielded more misleading internal fragments from the polyesteramides.…”

Fragmentation of deprotonated polyethylene glycols, [PEG – H]–

“…Highresolution mass spectrometry is useful for determining average molecular weight and composition, [1][2][3][4] while more advanced methods, such as collision-induced dissociation (CID), can yield structure and sequence information. [1,[5][6][7] Monomer structure and end-group functionalities of polymers often determine the most appropriate method for ion generation. Lewis base groups incorporated into a monomer attach protons, molecular, or metal cations and form singly or multiply charged ions, [8] while species with acidic groups lose protons to form negative ions.…”

Electron Transfer Dissociation of Doubly Charged Ions with Different Cationizing Agents

“…1,[3][4][5]7 More importantly, unlike CAD, ECD and ETD preserve posttranslational modifications and, thus, are widely used to identify such features. 3,7 ECD and ETD have been successfully applied to synthetic polymers as well, [8][9][10][11][12][13][14][15] where they cause fragmentation via pathways different from those occurring by CAD, leading to complementary structure information. 8,10,13,15 Both ECD and ETD require precursor ions with ≥2+ charges in order to generate mass spectrometrically observable species after electron capture (in ECD) or electron transfer (in ETD).…”

“…In the vast majority of previous studies, the multiply charged species subjected to ECD or ETD carried identical charges, provided by several units of the same cation, usually multiple protons or multiple sodium ions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] ETD 16 and ECD 17,18 on oligosaccharides charged by divalent metal ions has also been performed, as has ECD on synthetic peptoids carrying mixed proton and sodium charges. 19 Here, we report the first ETD study on a peptide and a modified polysaccharide ("glycopolymer") that were charged with different cations and compare the results with the ETD characteristics of the same analytes charged with identical cations.…”