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A predictive science approach to aid understanding of electrospray ionisation tandem mass spectrometric fragmentation pathways of small molecules using density functional calculations

A predictive science approach to aid understanding of electrospray ionisation tandem mass spectrometric fragmentation pathways of small molecules using density functional calculations
A predictive science approach to aid understanding of electrospray ionisation tandem mass spectrometric fragmentation pathways of small molecules using density functional calculations
RATIONALE: Tandem mass spectrometry (MS/MS) dissociation pathways can vary markedly between compound classes and can result in challenging and time-consuming interpretation of the data. Compound, class and substructure specific fragmentation rules for protonated molecules require refinement to aid the structural elucidation process.

METHODS: The application of a predictive science approach using density functional theory (DFT) calculations has been investigated to estimate the abundances of first-generation product ions observed using an ion trap mass spectrometer. This has been achieved by application of Boltzmann population theory to electrospray ionisation (ESI)-MS and MS/MS data.

RESULTS: Tandem ESI-MS data for this preliminary study were used to investigate the internal stabilities of protonated species and their product ions. The calculated relative abundances of 11.3%, 96.5%, and 1.1% for the product ion (m/z 192) of three quinazoline structural isomers are compared with the experimental values of 16%, 90% and 0% observed in the first-generation product ion mass spectra.

CONCLUSIONS: Close correlation between calculated and experimental data has been demonstrated for these initial data. Applying this approach and establishing fragmentation rules, based on structure specific and common fragmentation behaviour, would improve and expedite the structural elucidation process.
0951-4198
964-970
Galezowska, Angelika
cd23b43a-aa5e-40f4-8043-2875a0c5a86d
Harrison, Mark W.
096a57b2-3fff-431e-87e3-07c8434a8e52
Herniman, Julie M.
530b1a36-1386-4602-8df7-defa6eb3512b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Langley, G. John
7ac80d61-b91d-4261-ad17-255f94ea21ea
Galezowska, Angelika
cd23b43a-aa5e-40f4-8043-2875a0c5a86d
Harrison, Mark W.
096a57b2-3fff-431e-87e3-07c8434a8e52
Herniman, Julie M.
530b1a36-1386-4602-8df7-defa6eb3512b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Langley, G. John
7ac80d61-b91d-4261-ad17-255f94ea21ea

Galezowska, Angelika, Harrison, Mark W., Herniman, Julie M., Skylaris, Chris-Kriton and Langley, G. John (2013) A predictive science approach to aid understanding of electrospray ionisation tandem mass spectrometric fragmentation pathways of small molecules using density functional calculations. Rapid Communications in Mass Spectrometry, 27 (9), 964-970. (doi:10.1002/rcm.6536).

Record type: Article

Abstract

RATIONALE: Tandem mass spectrometry (MS/MS) dissociation pathways can vary markedly between compound classes and can result in challenging and time-consuming interpretation of the data. Compound, class and substructure specific fragmentation rules for protonated molecules require refinement to aid the structural elucidation process.

METHODS: The application of a predictive science approach using density functional theory (DFT) calculations has been investigated to estimate the abundances of first-generation product ions observed using an ion trap mass spectrometer. This has been achieved by application of Boltzmann population theory to electrospray ionisation (ESI)-MS and MS/MS data.

RESULTS: Tandem ESI-MS data for this preliminary study were used to investigate the internal stabilities of protonated species and their product ions. The calculated relative abundances of 11.3%, 96.5%, and 1.1% for the product ion (m/z 192) of three quinazoline structural isomers are compared with the experimental values of 16%, 90% and 0% observed in the first-generation product ion mass spectra.

CONCLUSIONS: Close correlation between calculated and experimental data has been demonstrated for these initial data. Applying this approach and establishing fragmentation rules, based on structure specific and common fragmentation behaviour, would improve and expedite the structural elucidation process.

Full text not available from this repository.

More information

Published date: 15 May 2013
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Business, Law and Art

Identifiers

Local EPrints ID: 356504
URI: http://eprints.soton.ac.uk/id/eprint/356504
ISSN: 0951-4198
PURE UUID: 857fbd6d-78dc-4f1a-9a57-ce29e1c56c37
ORCID for Julie M. Herniman: ORCID iD orcid.org/0000-0003-4834-1093
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433
ORCID for G. John Langley: ORCID iD orcid.org/0000-0002-8323-7235

Catalogue record

Date deposited: 01 Oct 2013 10:25
Last modified: 19 Nov 2019 02:01

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