Mapping formation pathways and end group patterns of stimuli-responsive polymer systems via high-resolution electrospray ionization mass spectrometry

Hart-Smith, G., Lovestead, T. M., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2007) Mapping formation pathways and end group patterns of stimuli-responsive polymer systems via high-resolution electrospray ionization mass spectrometry. Biomacromolecules, 8(8).

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Abstract

"Smart" polymers and polymer - protein conjugates find a vast array of biomedical applications. Ambient temperature reversible addition fragmentation chain transfer RAFT polymerizations conducted in an aqueous environment are a favorable method of choice for the synthesis of these materials; however, information regarding the initiation mechanisms behind these polymerizations - and thus the critical polymer end groups - is lacking. In the current study, high-resolution soft ionization mass spectrometry techniques were used to map the product species generated during ambient temperature γ-radiation induced RAFT polymerizations of N-isopropylacrylamide NIPAAm and acrylic acid AA in aqueous media, allowing the generated end groups to be unambiguously established. It was found that trithiocarbonate and •R radicals produced from the radiolysis of the RAFT agent, •OH and •OOH radicals produced from the radiolysis of water, and •H radicals produced from the radiolysis of water, RAFT agent, or monomer were capable of initiating polymerizations and thus contribute toward the generated chain ends. Additionally, thiol terminated chains were formed via degradation of trithiocarbonate end groups. The current study is the first to provide comprehensive mapping of the formation pathways and end group patterns of stimuli-responsive polymers, thus allowing the design and implementation of these materials to proceed in a more tailored fashion. © 2007 American Chemical Society.

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ID Code: 99148
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :24
Export Date: 5 September 2016
CODEN: BOMAF
Correspondence Address: Barner-kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia; email: c.barner-kowollik@unsw.edu.au
Chemicals/CAS: acrylic acid, 10344-93-1, 79-10-7; carbonic acid, 3812-32-6, 463-79-6; hydroxyl radical, 3352-57-6; poly(n isopropylacrylamide), 25189-55-3; Acrylamides; Acrylates; acrylic acid, 79-10-7; N-isopropylacrylamide, 2210-25-5; Polymers; Water, 7732-18-5
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Keywords: Acrylics, Degradation, Free radical polymerization, Monomers, Radiolysis, Temperature, High-resolution soft ionization mass spectrometry techniques, Stimuli-responsive polymers, Thiol terminated chains, Trithiocarbonate, Polymers, acrylic acid, biomaterial, carbonic acid, free radical, hydroxyl radical, poly(n isopropylacrylamide), polymer, radical, aqueous solution, article, biomedical engineering, chemical structure, electrospray mass spectrometry, enzyme degradation, fragmentation reaction, gamma radiation, polymerization, priority journal, synthesis, temperature sensitivity, thermostability, Acrylamides, Acrylates, Gamma Rays, Spectrometry, Mass, Electrospray Ionization, Water
DOI: 10.1021/bm700526j
ISSN: 15257797
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 06 Oct 2016 22:57

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