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Thermo-induced self-assembly of responsive poly(DMAEMA-b-DEGMA) block copolymers into multi- and unilamellar vesicles

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Pietsch, Christian, Mansfeld, Ulrich, Guerrero-Sanchez, Carlos, Hoeppener, Stephanie, Vollrath, Antje, Wagner, M. (Michael), Hoogenboom, Richard, Saubern, Simon, Thang, San H., Becer, C. Remzi, Chiefari, John and Schubert, U. (Ulrich) (2012) Thermo-induced self-assembly of responsive poly(DMAEMA-b-DEGMA) block copolymers into multi- and unilamellar vesicles. Macromolecules, Vol.45 (No.23). pp. 9292-9302. doi:10.1021/ma301867h ISSN 0024-9297 .

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Official URL: http://dx.doi.org/10.1021/ma301867h

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Abstract

A series of thermoresponsive diblock copolymers of poly[2-(dimethylamino)ethyl methacrylate-block-di(ethyleneglycol) methyl ether methacrylate], poly(DMAEMA-b-DEGMA), were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerizations. The series consist of diblock and quasi diblock copolymers. Sequential monomer addition was used for the quasi diblock copolymer synthesis and the macro-chain transfer approach was utilized for the block copolymer synthesis. The focus of this contribution is the controlled variation of the ratios of DMAEMA to DEGMA in the copolymer composition, resulting in a systematic polymer library. One of the investigated block copolymer systems showed double lower critical solution temperature (LCST) behavior in water and was further investigated. The phase transitions of this block copolymer were studied in aqueous solutions by turbidimetry, dynamic light scattering (DLS), variable temperature proton nuclear magnetic resonance (1H NMR) spectroscopy, zeta potential, and cryo transmission electron microscopy (cryo-TEM). The block copolymer undergoes a two-step thermo-induced self-assembly, which results in the formation of multilamellar vesicles after the first LCST temperature and to unilamellar vesicles above the second LCST transition. An interplay of ionic interactions as well as the change of the corresponding volume fraction during the LCST transitions were identified as the driving force for the double responsive behavior.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Self-assembly (Chemistry), Diblock copolymers, Coated vesicles, Polymerization
Journal or Publication Title: Macromolecules
Publisher: American Chemical Society
ISSN: 0024-9297
Official Date: 2012
Dates:
DateEvent
2012Published
Volume: Vol.45
Number: No.23
Page Range: pp. 9292-9302
DOI: 10.1021/ma301867h
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: Dutch Polymer Institute (DPI), Carl-Zeiss-Stiftung Jena, Commonwealth Scientific and Industrial Research Organization (Australia) (CSIRO)

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