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Copolymer analysis by mass spectrometry
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Town, James S. (2020) Copolymer analysis by mass spectrometry. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3752310
Abstract
Polymeric materials have many functions in the modern world. This is due to their tuneable thermal and mechanical properties, the ease at which they can be functionalised, and the scalability of the synthetic methods. Advances in polymer synthetic chemistry have allowed more exact design of these materials for their function, leading to a rise in the complexity of the products and properties available. As the need for more precise synthetic procedures increases as does the need for analysis techniques to characterise their products. Polymers by definition are complex mixtures which makes characterisation challenging.
Mass spectrometry is capable of rising to many of the challenges which polymer research presents. Many important features of polymers are capable of being determined by mass spectrometry such as, end groups, molecular weight, composition, and architecture. A commonly used technique for polymer mass spectrometry is matrix assisted laser/desorption time-of-flight mass spectrometry (MALDI-ToF-MS).
In this thesis the author presents 3 published works which seek to improve the molecular information which can be gained from polymer mass spectrometry research, with a focus on the determination of monomer sequencing in copolymer samples.
The first paper (chapter 2) shows a comparison between 2 commonly used tandem mass spectrometry MALDI-ToF techniques (MALDI-ToF/ToF), and their effect on the fragmentation species examined. These two techniques are post source decay (PSD) and collision-induced dissociation (CID). The methods are used on a variety of homopolymers, to examine the effect of different heteroatoms in the polymer backbone. It is found that PSD produces less fragments than CID in most of the homopolymers. The PSD fragments tend to be generated more often by rearrangements/fragmentation around the heteroatom, whereas CID will provide more fragments in carbon-carbon bonds 5
The second paper (chapter 3) is an investigation of PSD analysis of acrylate homopolymers and copolymers. The paper shows a fragmentation pathway which appears unique to the halide end group polymers. The paper also displays the qualitative differences between a diblock copolymer and a statistical copolymer, displaying the ease at which copolymer microstructure can be determined by tandem mass spectrometry. The diblock copolymer is then examined in more detail, displaying that there is a small amount of mixing discovered at the block boundary, despite the use of controlled radical polymerisation methods. This shows the powerful copolymer sequencing which can be provided by tandem mass spectrometry.
The third paper (chapter 4) is centred on the development of a generic algorithm for automatic peak assignment of copolymer MALDI-ToF data. This algorithm allows quick assignment of the monomer composition of each peak present in the spectra, producing a table of these results. This data can then be displayed as a heatmap of the two monomers where the colour is the intensity of the peak. Here qualitative differences can be seen between different copolymer compositions and different copolymer microstructures. This is an examination of the composition distribution, an often-neglected part of a copolymer sample.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry T Technology > TA Engineering (General). Civil engineering (General) |
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Library of Congress Subject Headings (LCSH): | Polymers, Polymers -- Spectra, Mass spectrometry, Tandem mass spectrometry, Fragmentation reactions | ||||
Official Date: | September 2020 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Haddleton, David M. | ||||
Sponsors: | Engineering and Physical Sciences Research Council ; AstraZeneca (Firm) ; Syngenta UK (Firm) | ||||
Format of File: | |||||
Extent: | [12 unnumbered leaves], 162 leaves : illustrations | ||||
Language: | eng |
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