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Stochasticity of poly(2-oxazoline) oligomer hydrolysis determined by tandem mass spectrometry

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Morgan, Tomos E., Floyd, Thomas G., Marzullo, Bryan P., Wootton, Christopher A., Barrow, Mark P., Bristow, Anthony W. T., Perrier, Sébastien and O'Connor, Peter B. (2022) Stochasticity of poly(2-oxazoline) oligomer hydrolysis determined by tandem mass spectrometry. Polymer Chemistry, 13 (28). pp. 4162-4169. doi:10.1039/d2py00437b ISSN 1759-9962.

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Official URL: https://doi.org/10.1039/d2py00437b

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Abstract

Understanding modification of synthetic polymer structures is necessary for their accurate synthesis and potential applications. In this contribution, a series of partially hydrolyzed poly(2-oxazoline) species were produced forming poly[(2-polyoxazoline)-co-(ethylenimine)] (P(EtOx-co-EI)) copolymers; EI being the hydrolyzed product of Ox. Bulk mass spectrometry (MS) measurements accurately measured the EI content. Tandem mass spectrometry analysis of the EI content in the copolymer samples determined the distribution of each monomer within the copolymer and corresponded to a theoretically modelled random distribution. The EI distribution across the polymers was shown to be effected by the choice of terminus, with a permanent hydrolysis event observed at an OH terminus. A neighbouring group effect wasn't observed at the polymer length analysed (approximately 25-mer species), suggesting that previously observed neighbouring group effects require a larger polymer chain. Although clearly useful for random polymer distribution this approach may be applied to many systems containing non-specific modifications to determine if they are directed or random locations across peptides, proteins, polymers, and nucleic acids.

Item Type: Journal Article
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Faculty of Science, Engineering and Medicine > Medicine > Warwick Medical School
SWORD Depositor: Library Publications Router
Journal or Publication Title: Polymer Chemistry
Publisher: Royal Society of Chemistry (RSC)
ISSN: 1759-9962
Official Date: 28 July 2022
Dates:
DateEvent
28 July 2022Published
2 June 2022Available
1 June 2022Accepted
Volume: 13
Number: 28
Page Range: pp. 4162-4169
DOI: 10.1039/d2py00437b
Status: Peer Reviewed
Publication Status: Published
Reuse Statement (publisher, data, author rights): ** Article version: VoR ** From Crossref journal articles via Jisc Publications Router ** Licence for VoR version of this article starting on 02-06-2022: http://creativecommons.org/licenses/by/3.0/
Access rights to Published version: Open Access (Creative Commons)
Date of first compliant deposit: 1 August 2022
Date of first compliant Open Access: 1 August 2022
Related URLs:
  • http://creativecommons.org/licenses/by/3...

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