Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 4, Pages 1279-1283Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201409799
Keywords
block copolymers; morphological transitions; nanoparticles; RAFT polymerization; self-assembly
Categories
Funding
- University of Sheffield
- GEO Specialty Chemicals
- ERC Advanced Investigator award [PISA 320372]
- EPSRC [EP/J007846/1, EP/K030949/1]
- Swiss National Science Foundation
- Engineering and Physical Sciences Research Council [EP/J007846/1, EP/K030949/1] Funding Source: researchfish
- EPSRC [EP/J007846/1, EP/K030949/1] Funding Source: UKRI
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A carboxylic acid based reversible additionfragmentation transfer (RAFT) agent is used to prepare gels composed of worm-like diblock copolymers using two non-ionic monomers, glycerol monomethacrylate (GMA) and 2-hydroxypropyl methacrylate (HPMA). Ionization of the carboxylic acid end-group on the PGMA stabilizer block induces a worm-to-sphere transition, which in turn causes immediate degelation. This morphological transition is fully reversible as determined by TEM and rheology studies and occurs because of a subtle change in the packing parameter for the copolymer chains. A control experiment where the methyl ester derivative of the RAFT agent is used to prepare the same diblock copolymer confirms that no pH-responsive behavior occurs in this case. This end-group ionization approach is important for the design of new pH-responsive copolymer nano-objects as, unlike polyacids or polybases, only a minimal amount of added base (or acid) is required to drive the morphological transition.
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