Mixed, multicompartment, or janus micelles? A systematic study of thermoresponsive bis-hydrophilic block terpolymers

Walther, A., Barner-Kowollik, C., & Müller, A. H. E. (2010) Mixed, multicompartment, or janus micelles? A systematic study of thermoresponsive bis-hydrophilic block terpolymers. Langmuir, 26(14).

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Abstract

We present a systematic investigation of the extent of compartmentalization in micelles formed by a series of bishydrophilic block terpolymers with two outer water-soluble segments. The corona blocks are constructed from poly(ethylene oxide) (PEO) and the thermoresponsive poly(N-isopropyl-acrylamide) (PNiPAAm). The fraction of PNiPAAm is varied to establish its influence on the supramicellar aggregation and corona phase behavior. We demonstrate that-when the collapse of PNiPAAm is triggered-a clustering of micelles into superstructures only occurs when the contour length of the thermoresponsive block is longer than that of the PEO chains. The volume fractions play a minor role. The extent of superstructure formation increases with the amount of heating cycles, pointing to a rearrangement of micelles with a mixed corona into a phase-segregated corona. The collapse of PNiPAAm is exploited to artificially raise the incompatibility and drive phase segregation. A uniform population of biphasic Janus micelles cannot be obtained. After repeated heating cycles, the mixture consists of a range of multicompartment architectures, whose patch distribution can be derived from aggregate structures found in cryo-TEM obtained at high temperature. In the last section, we relate our results to previously studied systems and attempt to derive some generalities. First, we try to answer the question of how likely it is in terms of thermodynamics to obtain truly selfassembled Janus micelles. Furthermore, our results can provide an estimation for the volume ratio or/and block lengths required in micelles composed out of two corona blocks to induce supramicellar aggregation when a hydrophilic-tohydrophobic phase transition is triggered in one of the blocks. © 2010 American Chemical Society.

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ID Code: 99256
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :45
Export Date: 5 September 2016
CODEN: LANGD
Correspondence Address: Walther, A.; Makromolekulare Chemie II and Bayreuther Zentrum für Kolloide und Grenzflächen, Universität Bayreuth, D-95440 Bayreuth, Germany; email: Andreas.walther@hut.fi
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Keywords: Acrylamides, Aggregate structures, Bi-Phasic, Block lengths, Block terpolymers, Contour lengths, cryo-TEM, Heating cycles, High temperature, Hydrophilic blocks, Janus micelles, Phase segregations, PNIPAAm, Self-assembled, Superstructure formation, Systematic investigations, Systematic study, Thermo-responsive, Volume ratio, Amides, Ethylene, Heating, Hydrogels, Hydrophilicity, Phase separation, Phase transitions, Polyethylene oxides, Thermodynamics, Micelles
DOI: 10.1021/la101173b
ISSN: 07437463
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: 07 Oct 2016 03:29

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