Self-assembly of Hydrophilic Homopolymers A Matter of End Groups.pdf (971.67 kB)
Self-assembly of hydrophilic homopolymers: a matter of RAFT end groups
journal contribution
posted on 2016-10-17, 13:43 authored by Jianzhong Du, Helen WillcockHelen Willcock, Joseph P. Patterson, Ian Portman, Rachel K. O'ReillyUnusual self-assembly behavior is observed for a range of hydrophilic homopolymers. This self-assembly behavior is contrary to the expected behavior of such hydrophilic polymers and instead mimics more commonly reported amphiphilic block copolymers. It is proposed that the unique combination of hydrophobic end groups at both the α and Ω chain end accounts for this unusual self-assembly behavior. Complex internal polymer micelles are spontaneously formed when hydrophilic homopolymer polyelectrolytes and neutral polymers (with a weight fraction of the hydrophobic end groups <10 wt%) are directly dissolved in water. The homopolymers, poly[2-(diethylamino)ethyl methacrylate], poly(N-isopropylacrylamide), and poly(ethoxyethylacrylate) are synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization using S′-1-dodecyl-(S′)-(α,α′- dimethyl-α″-acetic acid) trithiocarbonate (DDMAT) and its derivatives as chain transfer agents (CTAs). A range of polyelectrolyte homopolymers with different terminal groups are designed and synthesized, which under acidic aqueous solution direct the self-assembly to form well-defined nanostructures. This assembly behavior was also observed for neutral polymers, and it was determined that the structure of the hydrophobic end groups (and thus choice of RAFT CTA) are very important in facilitating this unusual self-assembly behavior of hydrophilic homopolymers. It is proposed that the functionality of commonly used CTAs such as DDMAT, can affect the solution association of the resultant homopolymers and can in fact afford ABA′ type polymers, which can undergo self-assembly to form higher-order nanostructures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Funding
The Leverhulme Trust is thanked for a post-doctoral fellowship for J.D. The EPSRC and Royal Society are thanked for support for R.K.O.R. The GPC used in this research was ... part-funded by the European Regional Development Fund (ERDF).
History
School
- Aeronautical, Automotive, Chemical and Materials Engineering
Department
- Materials
Published in
SmallVolume
7Issue
14Pages
2070 - 2080Citation
DU, J. ... et al., 2011. Self-assembly of hydrophilic homopolymers: a matter of RAFT end groups. Small, 7 (14), pp.2070-2080.Publisher
© Wiley-VCHVersion
- AM (Accepted Manuscript)
Publisher statement
This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/Publication date
2011Notes
This is the peer reviewed version of the following article: DU, J. ... et al., 2011. Self-assembly of hydrophilic homopolymers: a matter of RAFT end groups. Small, 7 (14), pp.2070-2080, which has been published in final form at: http://dx.doi.org/10.1002/smll.201100382. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.ISSN
1613-6810eISSN
1613-6829Publisher version
Language
- en