Tandem Mass Spectrometry Analysis of Polymer Structures and Architectures

Scionti, Vincenzo; Wesdemiotis, Chrys

doi:10.1002/9783527641826.ch3

Cited by 18 publications

(21 citation statements)

References 75 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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“…Under the low-energy CAD conditions used in this study, multiple collisions occur before fragmentation. The internal energy deposited in each collision is redistributed throughout the whole molecule, until enough internal energy has been accumulated to induce fragmentation within the time spent in the collision cell [94]. This slow increase of bn or bn* fragments.…”

Section: Instrumental Conditionsmentioning

confidence: 99%

Characterization of supramolecular peptide-polymer bioconjugates using multistage tandem mass spectrometry

Wei

Gerişlioğlu

Atakay

et al. 2019

International Journal of Mass Spectrometry

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Mass spectrometry (MS) is an essential analytical tool for the characterization of the structure of biological macromolecules, including protein-protein and protein-ligand complexes. One-dimensional MS separates gas-phase analyte ions based on their mass to charge ratio (m/z); however, to obtain more detailed structural information, tandem MS (MS/MS), which involves isolation and subsequent fragmentation of a precursor ion, is required.In this thesis, electrospray ionization multistage tandem mass spectrometry (ESI-MS n ) was employed to examine the non-covalent complexes between poly(styrene sulfonate) (PSS) and poly-L-lysine (PLL). During single-stage ion activation, the PLL peptide chain mainly underwent backbone cleavages without disruption of the noncovalent interaction which could only be broken via sequential application of electron transfer dissociation (ETD) and collisionally activated dissociation (CAD), indicating strong binding interactions between the two polyelectrolyte chains. Such binding properties make PSS a potential "non-covalent (supramolecular) label" for determining the surface accessibility of basic residues on a peptide or protein. To probe this premise, noncovalent complexes of substance P and PSS were characterized by ESI-MS n using different ion activation methods. Both MS 2 and MS 3 experiments on the substance P + PSS complex resulted in the formation of bn (on CAD) or cn (on ETD) fragments attached non-covalently to the intact PSS chain. All peptide fragments containing the intact PSS chain included Arg1, Lys3, and Gln5, pointing out that these residues, which are located near the Nterminus, are most likely involved in the noncovalent interaction with PSS. In contrast, iv Gln6 was excluded from this fragment series, attesting a much weaker interaction with PSS due to lesser accessibility. The strong tendency of PSS to bind peptides noncovalently at sites that can be elucidated by MS n demonstrates a proof-of-concept for the capacity of this approach to unveil higher order structure in proteins.

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“…The UltraFlex III TOF/TOF mass spectrometer is composed of a short linear TOF tube, interfaced axially with a reflectron TOF device [43,44]. MS 2 spectra were acquired using the LIFT technique, which involves raising the laser intensity to induce fragmentation in the linear TOF part, isolation of the desired precursor ion and its fragments ("ion family") by a high-resolution timed ion selector (TIS), and post-acceleration ("lifting") of the selected ion family for mass analysis in the reflectron TOF segment.…”

Section: Ms and Msmentioning

confidence: 99%

Differentiation of Linear and Cyclic Polymer Architectures by MALDI Tandem Mass Spectrometry (MALDI-MS²)

Yol

Dabney

Wang

et al. 2012

J. Am. Soc. Mass Spectrom.

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Tandem Mass Spectrometry Analysis of Polymer Structures and Architectures

Cited by 18 publications

References 75 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 supramolecular peptide-polymer bioconjugates using multistage tandem mass spectrometry

Differentiation of Linear and Cyclic Polymer Architectures by MALDI Tandem Mass Spectrometry (MALDI-MS²)

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Tandem Mass Spectrometry Analysis of Polymer Structures and Architectures

Cited by 18 publications

References 75 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 supramolecular peptide-polymer bioconjugates using multistage tandem mass spectrometry

Differentiation of Linear and Cyclic Polymer Architectures by MALDI Tandem Mass Spectrometry (MALDI-MS2)

Contact Info

Product

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Differentiation of Linear and Cyclic Polymer Architectures by MALDI Tandem Mass Spectrometry (MALDI-MS²)