Journal article
A combined theoretical and experimental study of mechanisms of fragmentation active for PHB oligomers in negative-ion mode multistage mass spectrometry
International journal of mass spectrometry, v 304(1)
15 Jun 2011
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
First-principles studies of the potential energy profiles for dissociation of poly[(R, S)-3-hydroxybutanoic acid] [PHBn-H](-) anions by proton rearrangement and direct fragmentation, as well as subsequent statistical RRKM analysis, indicate that fragmentation should proceed mainly through successive loss of a single 86 Da neutral unit (propene + CO2). This theoretically predicted fragmentation mechanism is inconsistent with that proposed in the literature based on experiments, which suggests that proton rearrangements are the only active fragmentation channels in CID of [PHBn-H](-). We have combined experimental ESI-MS/MS fragmentation studies of [PHBn-H](-) with first-principles explorations of the potential energy surfaces, and molecular dynamics simulations of CID and thermal fragmentation events to understand this discordance. Both proton rearrangement and direct fragmentation channels are considered. The results reveal that the fragmentations observed at low collision energy favor the direct fragmentation channel and are more closely modeled as a thermal fragmentation process. By contrast, fragmentations observed at higher collision energy favor the indirect fragmentation channels and are more closely modeled as a fast CID process. (C) 2011 Elsevier B.V. All rights reserved.
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Details
- Title
- A combined theoretical and experimental study of mechanisms of fragmentation active for PHB oligomers in negative-ion mode multistage mass spectrometry
- Creators
- Henryk Bednarski - Centre of Polymer and Carbon MaterialsKarl Sohlberg - Drexel UniversityMarian Domanski - Centre of Polymer and Carbon MaterialsJan Weszka - Centre of Polymer and Carbon MaterialsGrazyna Adamus - Centre of Polymer and Carbon MaterialsMarek Kowalczuk - Centre of Polymer and Carbon MaterialsVasile Cozan - Petru Poni Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41 A, 700487 Iasi, Romania
- Publication Details
- International journal of mass spectrometry, v 304(1)
- Publisher
- Elsevier
- Number of pages
- 10
- Grant note
- FP7-KBBE-2009-3-245084 / EU; European Commission
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000292349600003
- Scopus ID
- 2-s2.0-79958062175
- Other Identifier
- 991019168642104721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Physics, Atomic, Molecular & Chemical
- Spectroscopy