Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry
Thesis (M.Sc.)--Memorial University of Newfoundland, 2010. Chemistry Includes bibliographical references (leaves 114-131) The gas-phase fragmentation of a series of commercially available biotinyl reagents have been evaluated by electrospay ionization mass spectrometry (ESI-MS) and collision induced...
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ftmemorialunivdc:oai:collections.mun.ca:theses4/58063 2023-05-15T17:23:33+02:00 Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry Sioud, Salim. Memorial University of Newfoundland. Dept. of Chemistry 2010. xix, 146 leaves : ill. Image/jpeg; Application/pdf http://collections.mun.ca/cdm/ref/collection/theses4/id/58063 Eng eng Electronic Theses and Dissertations (15.78 MB) -- http://collections.mun.ca/PDFs/theses/Sioud_Salim.pdf a3496885 http://collections.mun.ca/cdm/ref/collection/theses4/id/58063 The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. Paper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries Biotin--Derivatives Fragmentation reactions Oligosaccharides--Analysis Tandem mass spectrometry Text Electronic thesis or dissertation 2010 ftmemorialunivdc 2015-08-06T19:22:05Z Thesis (M.Sc.)--Memorial University of Newfoundland, 2010. Chemistry Includes bibliographical references (leaves 114-131) The gas-phase fragmentation of a series of commercially available biotinyl reagents have been evaluated by electrospay ionization mass spectrometry (ESI-MS) and collision induced dissociation tandem mass spectrometry (CID-MS/MS) analyses using a QqTOF-MS/MS hybrid instrument. In general it has been observed that the CID-MS/MS fragmentation routes of the five precursor protonated molecules obtained from the biotin linkers I-5 afforded a series of product ions formed essentially by similar routes. The genesis and structural identities of all the product ions obtained from the biotin linkers I-5 have been assigned. All of the exact mass assignments of the protonated molecules and the product ions were verified by conducting separate CID-MS/MS analysis of the deuterium labeled precursor ions. -- The ESI-QqTOF-MS structural eluciadation of the core oligosaccharide of Aeromonas hydrophila (chemotype II) lipopolysaccharide has been investigated and it was demonstrated that it contained a 4-O-linked posphorylated group Kdo residue which was glycosylated by the remaining outer core oligosaccharide through its O-5 position. After, releasing the core oligosaccharide from the native LPS with acid, the phosphorylated Kdo residue eliminated phosphoric acid to produce a core oligosaccharide containing a mixture of diastereomeric 4,8- and 4,7-anhydro-α-keto acids and an open olefinic Kdo residue. The characteristic glycone sequence was elucidated by CID-MS/MS of the protonated molecule of the native core oligosaccharide. In addition, the analysis of the Hakamori permethylated core oligosaccharide was carried out by ESI-QqTOF-MS and MALDI-TOF-MS analyses. The presence of more than nine isobaric isomers of this core was noticed. The collision-induced dissociation analysis (CID-MS/MS) of the various protonated permethylated core oligosaccharide molecules showed a similar and diagnostic fragmentation pattern. -- To confirm these obtained results, the permethylation of the core oligosaccharide SJ-48R has been performed with a different methylation method (Ciucanu & Kerek method). It was realized that the extra minor satellite signals obtained in the ESI-QqTOF-MS and MALDI-TOF-MS analyses were DMSO stable covalent addition products, which have occurred by a Michael addition on the 4,8-Kdo exocyclic double bond and on the C-3-C-4 double bond of the olefinic open-chain Kdo residue. To our knowledge, this is the first time that DMSO adducts have been observed in the gas phase, and they have never before been reported. Thesis Newfoundland studies University of Newfoundland Memorial University of Newfoundland: Digital Archives Initiative (DAI) |
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Memorial University of Newfoundland: Digital Archives Initiative (DAI) |
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ftmemorialunivdc |
language |
English |
topic |
Biotin--Derivatives Fragmentation reactions Oligosaccharides--Analysis Tandem mass spectrometry |
spellingShingle |
Biotin--Derivatives Fragmentation reactions Oligosaccharides--Analysis Tandem mass spectrometry Sioud, Salim. Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry |
topic_facet |
Biotin--Derivatives Fragmentation reactions Oligosaccharides--Analysis Tandem mass spectrometry |
description |
Thesis (M.Sc.)--Memorial University of Newfoundland, 2010. Chemistry Includes bibliographical references (leaves 114-131) The gas-phase fragmentation of a series of commercially available biotinyl reagents have been evaluated by electrospay ionization mass spectrometry (ESI-MS) and collision induced dissociation tandem mass spectrometry (CID-MS/MS) analyses using a QqTOF-MS/MS hybrid instrument. In general it has been observed that the CID-MS/MS fragmentation routes of the five precursor protonated molecules obtained from the biotin linkers I-5 afforded a series of product ions formed essentially by similar routes. The genesis and structural identities of all the product ions obtained from the biotin linkers I-5 have been assigned. All of the exact mass assignments of the protonated molecules and the product ions were verified by conducting separate CID-MS/MS analysis of the deuterium labeled precursor ions. -- The ESI-QqTOF-MS structural eluciadation of the core oligosaccharide of Aeromonas hydrophila (chemotype II) lipopolysaccharide has been investigated and it was demonstrated that it contained a 4-O-linked posphorylated group Kdo residue which was glycosylated by the remaining outer core oligosaccharide through its O-5 position. After, releasing the core oligosaccharide from the native LPS with acid, the phosphorylated Kdo residue eliminated phosphoric acid to produce a core oligosaccharide containing a mixture of diastereomeric 4,8- and 4,7-anhydro-α-keto acids and an open olefinic Kdo residue. The characteristic glycone sequence was elucidated by CID-MS/MS of the protonated molecule of the native core oligosaccharide. In addition, the analysis of the Hakamori permethylated core oligosaccharide was carried out by ESI-QqTOF-MS and MALDI-TOF-MS analyses. The presence of more than nine isobaric isomers of this core was noticed. The collision-induced dissociation analysis (CID-MS/MS) of the various protonated permethylated core oligosaccharide molecules showed a similar and diagnostic fragmentation pattern. -- To confirm these obtained results, the permethylation of the core oligosaccharide SJ-48R has been performed with a different methylation method (Ciucanu & Kerek method). It was realized that the extra minor satellite signals obtained in the ESI-QqTOF-MS and MALDI-TOF-MS analyses were DMSO stable covalent addition products, which have occurred by a Michael addition on the 4,8-Kdo exocyclic double bond and on the C-3-C-4 double bond of the olefinic open-chain Kdo residue. To our knowledge, this is the first time that DMSO adducts have been observed in the gas phase, and they have never before been reported. |
author2 |
Memorial University of Newfoundland. Dept. of Chemistry |
format |
Thesis |
author |
Sioud, Salim. |
author_facet |
Sioud, Salim. |
author_sort |
Sioud, Salim. |
title |
Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry |
title_short |
Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry |
title_full |
Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry |
title_fullStr |
Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry |
title_full_unstemmed |
Gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry |
title_sort |
gas-phase fragmentation studies of a series of biotin derivatives and of a core oligosaccharide by tandem mass spectrometry |
publishDate |
2010 |
url |
http://collections.mun.ca/cdm/ref/collection/theses4/id/58063 |
genre |
Newfoundland studies University of Newfoundland |
genre_facet |
Newfoundland studies University of Newfoundland |
op_source |
Paper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries |
op_relation |
Electronic Theses and Dissertations (15.78 MB) -- http://collections.mun.ca/PDFs/theses/Sioud_Salim.pdf a3496885 http://collections.mun.ca/cdm/ref/collection/theses4/id/58063 |
op_rights |
The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. |
_version_ |
1766113252530454528 |