Tandem Mass Spectrometry and Polymer Ion Dissociation

Polce, Michael J.; Wesdemiotis, Chrys

doi:10.1002/9780470567234.ch5

Cited by 10 publications

(13 citation statements)

References 179 publications

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“…The characterization of such polymers by mass spectrometry (MS) has significantly improved after the discovery of soft ionization techniques, in particular matrix‐assisted laser desorption ionization and electrospray ionization (ESI), which enable the detection and analysis of each component of the polymeric analyte . The development of instruments with tandem mass spectrometry (MS 2 ) capabilities has further made it possible to obtain detailed information related to the polymer connectivity and architecture . The most common technique used to perform MS 2 analysis of polymers is collisionally activated dissociation (CAD).…”

Section: Introductionmentioning

confidence: 99%

“…[14][15][16][17] The development of instruments with tandem mass spectrometry (MS 2 ) capabilities has further made it possible to obtain detailed information related to the polymer connectivity and architecture. [18][19][20][21][22][23][24] The most common technique used to perform MS 2 analysis of polymers is collisionally activated dissociation (CAD). In the last decade, other fragmentation techniques have been developed, such as electron capture dissociation (ECD) [25][26][27] and the closely related electron transfer dissociation (ETD), [28][29][30][31][32] which employ ion-electron or ion-ion reactions, respectively, as ion excitation method rather than collisions with neutral targets.…”

Section: Introductionmentioning

confidence: 99%

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Electron transfer dissociation versus collisionally activated dissociation of cationized biodegradable polyesters

Scionti

Wesdemiotis

2012

J. Mass. Spectrom.

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Biodegradable polyesters were ionized by electrospray ionization and characterized by tandem mass spectrometry using collisionally activated dissociation (CAD) and electron transfer dissociation (ETD) as activation methods. The compounds studied include one homopolymer, polylactide and two copolymers, poly(ethylene adipate) and poly(butylene adipate). CAD of [M+2Na](2+) ions from these polyesters proceeds via charge-remote 1,5-H rearrangements over the ester groups, leading to cleavages at the (CO)O-alkyl bonds. ETD of the same precursor ions creates a radical anion at the site of electron attachment, which fragments by radical-induced cleavage of the (CO)O-alkyl bonds and by intramolecular nucleophilic substitution at the (CO)-O bonds. In contrast to CAD, ETD produces fragments in one charge state only and does not cause consecutive fragmentations, which simplifies spectral interpretation and permits conclusive identification of the correct end groups. The radical-site reactions occurring during ETD are very similar with those reported for ETD of protonated peptides. Unlike multiply protonated species, multiply sodiated precursors form ion pairs (salt bridges) after electron transfer, thereby promoting dissociations via nucleophilic displacement in addition to the radical-site dissociations typical in ETD.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electron transfer dissociation versus collisionally activated dissociation of cationized biodegradable polyesters

Scionti

Wesdemiotis

2012

J. Mass. Spectrom.

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“…The ‘series K n ’ has, in general, the lowest abundance and corresponds to H 2 N–(CH 2 CH 2 NH) x –H loses from two chain ends of the precursor ions. Scheme explains the used nomenclature.…”

Section: Resultsmentioning

confidence: 99%

Characterization of polyethylenimine by electrospray ionization and matrix-assisted laser desorption/ionization

Rivera-Tirado

Wesdemiotis

2011

J. Mass Spectrom.

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Branched polyethylenimines (PEIs) with lower average molecular weights (600, 1200 and 1800 Da) have been studied by Electrospray Ionization (ESI) and Matrix-Assisted Laser Desorption/Ionization (MALDI) mass spectrometry. In both, ESI and MALDI mass spectra, the main distribution arises from protonated PEI oligomers with NH(2) end groups, [PEI + H](+), which are observed at m/z 43n + 18. A trace of sodium contamination in the PEI samples results in the presence of a series that appears at m/z 43n + 40 [PEI + Na](+). However, only the MALDI mass spectra show a [PEI + K](+) series at m/z 43n + 56, because of matrix contamination with potassium, and a series generated by condensation of the matrix with PEI at m/z 43n + 30. Collisionally activated dissociation tandem mass spectrometry (CAD (MS/MS)) of protonated PEI oligomers is shown to yield three fragment ion series b(n), cn″ and K(n). The experiments have demonstrated the capabilities of these mass spectrometry techniques, along with CAD MS/MS to detect and characterize such polar synthetic polymers.

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“…The most widely used technique in synthetic polymer analyses has undoubtedly been collisionally activated dissociation (CAD) [2,3]. We recently reported the first MS 2 study using electron transfer dissociation (ETD), which was applied to the characterization of biodegradable polyesters [4].…”

Section: Introductionmentioning

confidence: 99%

Electron transfer dissociation of sodium cationized polyesters: Reaction time effects and combination with collisional activation and ion mobility separation

Katzenmeyer

Cool

Williams

et al. 2015

International Journal of Mass Spectrometry

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Tandem Mass Spectrometry and Polymer Ion Dissociation

Cited by 10 publications

References 179 publications

Electron transfer dissociation versus collisionally activated dissociation of cationized biodegradable polyesters

Electron transfer dissociation versus collisionally activated dissociation of cationized biodegradable polyesters

Characterization of polyethylenimine by electrospray ionization and matrix-assisted laser desorption/ionization

Electron transfer dissociation of sodium cationized polyesters: Reaction time effects and combination with collisional activation and ion mobility separation

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