Unified Fragmentation Pathways of Lithiated, Longer-Chain Acylglycerols Can Be Identified from Tandem Mass Spectrometry and Density Functional Computations.
Saved in:
| Title: | Unified Fragmentation Pathways of Lithiated, Longer-Chain Acylglycerols Can Be Identified from Tandem Mass Spectrometry and Density Functional Computations. |
|---|---|
| Authors: | Grossert, J. Stuart1 (AUTHOR) J.S.Grossert@dal.ca, Ramaley, Louis1 (AUTHOR) |
| Source: | Journal of the American Society for Mass Spectrometry. 2/5/2024, Vol. 36 Issue 2, p368-378. 11p. |
| Abstract: | We extend our previous work on the energetics and mechanisms of fragmentation in the mass spectrometry of triacylglycerols (TAGs). Previously, we proposed viable mechanisms for the collision-induced fragmentation of lithiated tripropionylglycerol using triple-quadrupole mass spectrometry. In this work, we used a QqLIT mass spectrometer to study both double- and triple-stage spectra from a range of TAGs having acid chains of types AAA (identical acid chains), AAB, ABA, and ABC, with chain lengths of 6–18 carbon atoms; we also studied some TAGs having a single double bond in the Δ-9 position. Detailed computations on fragmentation pathways were carried out on lithiated trihexanoylglycerol and on a limited number of longer chain ions. Second-stage fragmentations led to the formation of a lithiated ion after the loss of a neutral acid. With a further input of energy, this ion could rearrange into two other ions, one being formed more easily than the other. In a triple-stage fragmentation, these three ions give a defined series of product ions, some of which are characteristic of the substitution pattern on the glycerol core of the TAG. Computed reaction energies for product ion formation showed comparable trends to the relative intensities of the observed product ion spectra. These results have enabled us to propose unified mechanisms for the double- and triple-stage fragmentation of lithiated TAGs. The mechanisms have reasonable energetics, and all ions, as well as saddle points, have viable geometries. In addition, the fragmentation mechanisms are in accord with all the published experimental mass spectra. [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: 182829325 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Unified Fragmentation Pathways of Lithiated, Longer-Chain Acylglycerols Can Be Identified from Tandem Mass Spectrometry and Density Functional Computations. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Grossert%2C+J%2E+Stuart%22">Grossert, J. Stuart</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> J.S.Grossert@dal.ca</i><br /><searchLink fieldCode="AR" term="%22Ramaley%2C+Louis%22">Ramaley, Louis</searchLink><relatesTo>1</relatesTo> (AUTHOR) – 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>. 2/5/2024, Vol. 36 Issue 2, p368-378. 11p. – Name: Abstract Label: Abstract Group: Ab Data: We extend our previous work on the energetics and mechanisms of fragmentation in the mass spectrometry of triacylglycerols (TAGs). Previously, we proposed viable mechanisms for the collision-induced fragmentation of lithiated tripropionylglycerol using triple-quadrupole mass spectrometry. In this work, we used a QqLIT mass spectrometer to study both double- and triple-stage spectra from a range of TAGs having acid chains of types AAA (identical acid chains), AAB, ABA, and ABC, with chain lengths of 6–18 carbon atoms; we also studied some TAGs having a single double bond in the Δ-9 position. Detailed computations on fragmentation pathways were carried out on lithiated trihexanoylglycerol and on a limited number of longer chain ions. Second-stage fragmentations led to the formation of a lithiated ion after the loss of a neutral acid. With a further input of energy, this ion could rearrange into two other ions, one being formed more easily than the other. In a triple-stage fragmentation, these three ions give a defined series of product ions, some of which are characteristic of the substitution pattern on the glycerol core of the TAG. Computed reaction energies for product ion formation showed comparable trends to the relative intensities of the observed product ion spectra. These results have enabled us to propose unified mechanisms for the double- and triple-stage fragmentation of lithiated TAGs. The mechanisms have reasonable energetics, and all ions, as well as saddle points, have viable geometries. In addition, the fragmentation mechanisms are in accord with all the published experimental mass spectra. [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=182829325 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/jasms.4c00423 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 11 StartPage: 368 Titles: – TitleFull: Unified Fragmentation Pathways of Lithiated, Longer-Chain Acylglycerols Can Be Identified from Tandem Mass Spectrometry and Density Functional Computations. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Grossert, J. Stuart – PersonEntity: Name: NameFull: Ramaley, Louis IsPartOfRelationships: – BibEntity: Dates: – D: 05 M: 02 Text: 2/5/2024 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 10440305 Numbering: – Type: volume Value: 36 – Type: issue Value: 2 Titles: – TitleFull: Journal of the American Society for Mass Spectrometry Type: main |
| ResultId | 1 |
