Rearrangements Leading to Fragmentations of Hydrocinnamate and Analogous Nitrogen-Containing Anions Upon Collision-Induced Dissociation.
Saved in:
| Title: | Rearrangements Leading to Fragmentations of Hydrocinnamate and Analogous Nitrogen-Containing Anions Upon Collision-Induced Dissociation. |
|---|---|
| Authors: | Gillis, Elizabeth1, Grossert, J.1, White, Robert1 robert.white@dal.ca |
| Source: | Journal of the American Society for Mass Spectrometry. Mar2014, Vol. 25 Issue 3, p388-397. 10p. |
| Subjects: | Rearrangements (Chemistry), Fragmentation reactions, Collision induced dissociation, Tandem mass spectrometry, Decarboxylation, Dissociation (Chemistry) |
| Abstract: | Tandem mass spectrometry (MS/MS) confirmed decarboxylation as the major collision-induced dissociation (CID) pathway of deprotonated hydrocinnamic acid (CHCHCHCOH), N-phenylglycine (CHNHCHCOH) and 3-pyridin-2-ylpropanoic acid (CHNCHCHCOH). The structure and stability of isomeric precursor and product anions were examined using density functional theory and ab initio methods. Geometry optimizations and frequency calculations were performed using the B3LYP/6-31++G(2d,p) level of theory and basis set with additional single point energies calculated at the MP2/6-311++G(2d,p) level. The formation of a delocalized product anion by carboxyl group-mediated migration of a benzylic proton to the ortho position of the ring and subsequent C-CO bond cleavage was energetically more favorable than direct decarboxylation and rearrangements of anions within ion-neutral complexes with carbon dioxide. The energy barrier for rearrangement of the delocalized product anion to the more stable benzylic anion was lowest in the fragmentation pathway of 3-pyridin-2-ylpropanoate. More energetically demanding fragmentation processes were indicated by the formation of other product anions at higher collision energy. Computations supported the feasibility of the formation of hydroxycarbonyl, styrene, and phenide ions from the benzylic anion of hydrocinnamate and the corresponding product anions from the nitrogen-containing analogues. The loss of dihydrogen from decarboxylated 3-pyridin-2-ylpropanoate was characterized computationally as hydride abstraction of an aryl proton. Overall, the results highlight the importance of exploring rearrangements in the fragmentation pathways of ions formed by electrospray ionization (ESI). [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of the American Society for Mass Spectrometry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
|---|---|
| Header | DbId: egs DbLabel: Engineering Source An: 94355214 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Rearrangements Leading to Fragmentations of Hydrocinnamate and Analogous Nitrogen-Containing Anions Upon Collision-Induced Dissociation. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Gillis%2C+Elizabeth%22">Gillis, Elizabeth</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Grossert%2C+J%2E%22">Grossert, J.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22White%2C+Robert%22">White, Robert</searchLink><relatesTo>1</relatesTo><i> robert.white@dal.ca</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Society+for+Mass+Spectrometry%22">Journal of the American Society for Mass Spectrometry</searchLink>. Mar2014, Vol. 25 Issue 3, p388-397. 10p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Rearrangements+%28Chemistry%29%22">Rearrangements (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Fragmentation+reactions%22">Fragmentation reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Collision+induced+dissociation%22">Collision induced dissociation</searchLink><br /><searchLink fieldCode="DE" term="%22Tandem+mass+spectrometry%22">Tandem mass spectrometry</searchLink><br /><searchLink fieldCode="DE" term="%22Decarboxylation%22">Decarboxylation</searchLink><br /><searchLink fieldCode="DE" term="%22Dissociation+%28Chemistry%29%22">Dissociation (Chemistry)</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Tandem mass spectrometry (MS/MS) confirmed decarboxylation as the major collision-induced dissociation (CID) pathway of deprotonated hydrocinnamic acid (CHCHCHCOH), N-phenylglycine (CHNHCHCOH) and 3-pyridin-2-ylpropanoic acid (CHNCHCHCOH). The structure and stability of isomeric precursor and product anions were examined using density functional theory and ab initio methods. Geometry optimizations and frequency calculations were performed using the B3LYP/6-31++G(2d,p) level of theory and basis set with additional single point energies calculated at the MP2/6-311++G(2d,p) level. The formation of a delocalized product anion by carboxyl group-mediated migration of a benzylic proton to the ortho position of the ring and subsequent C-CO bond cleavage was energetically more favorable than direct decarboxylation and rearrangements of anions within ion-neutral complexes with carbon dioxide. The energy barrier for rearrangement of the delocalized product anion to the more stable benzylic anion was lowest in the fragmentation pathway of 3-pyridin-2-ylpropanoate. More energetically demanding fragmentation processes were indicated by the formation of other product anions at higher collision energy. Computations supported the feasibility of the formation of hydroxycarbonyl, styrene, and phenide ions from the benzylic anion of hydrocinnamate and the corresponding product anions from the nitrogen-containing analogues. The loss of dihydrogen from decarboxylated 3-pyridin-2-ylpropanoate was characterized computationally as hydride abstraction of an aryl proton. Overall, the results highlight the importance of exploring rearrangements in the fragmentation pathways of ions formed by electrospray ionization (ESI). [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of the American Society for Mass Spectrometry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=94355214 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1007/s13361-013-0788-5 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 10 StartPage: 388 Subjects: – SubjectFull: Rearrangements (Chemistry) Type: general – SubjectFull: Fragmentation reactions Type: general – SubjectFull: Collision induced dissociation Type: general – SubjectFull: Tandem mass spectrometry Type: general – SubjectFull: Decarboxylation Type: general – SubjectFull: Dissociation (Chemistry) Type: general Titles: – TitleFull: Rearrangements Leading to Fragmentations of Hydrocinnamate and Analogous Nitrogen-Containing Anions Upon Collision-Induced Dissociation. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Gillis, Elizabeth – PersonEntity: Name: NameFull: Grossert, J. – PersonEntity: Name: NameFull: White, Robert IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 03 Text: Mar2014 Type: published Y: 2014 Identifiers: – Type: issn-print Value: 10440305 Numbering: – Type: volume Value: 25 – Type: issue Value: 3 Titles: – TitleFull: Journal of the American Society for Mass Spectrometry Type: main |
| ResultId | 1 |
