Self-Assembly of Well-Defined Amphiphilic Polymeric Miktoarm Stars, Dendrons, and Dendrimers in Water: The Effect of Architecture

Lonsdale, D.E., Whittaker, M.R. and Monteiro, M.J. (2009) Self-Assembly of Well-Defined Amphiphilic Polymeric Miktoarm Stars, Dendrons, and Dendrimers in Water: The Effect of Architecture. Journal of Polymer Science. Part A, Polymer Chemistry, 47 22: 6292-6303. doi:10.1002/pola.23672


Author Lonsdale, D.E.
Whittaker, M.R.
Monteiro, M.J.
Title Self-Assembly of Well-Defined Amphiphilic Polymeric Miktoarm Stars, Dendrons, and Dendrimers in Water: The Effect of Architecture
Journal name Journal of Polymer Science. Part A, Polymer Chemistry   Check publisher's open access policy
ISSN 0887-624X
Publication date 2009-11-15
Year available 2009
Sub-type Article (original research)
DOI 10.1002/pola.23672
Volume 47
Issue 22
Start page 6292
End page 6303
Total pages 12
Editor Mitsuo Sawamoto
Place of publication Hoboken, N.J. USA
Publisher John Wiley & Sons, Inc.
Collection year 2010
Language eng
Subject C1
870303 Polymeric Materials (e.g. Paints)
030305 Polymerisation Mechanisms
Abstract Five polymeric architectures with a systematic increase in architectural complexity were synthesized by "click" reactions from a toolbox of functional linear polymers and small molecule linkers. The amphiphilic architectures ranged from a simple 3-miktoarm star block copolymer to the more complex third generation dendrimer-like block copolymer, consisting of polystyrene (PSTY) and polyacrylic acid (PAA). Micellization of these architectures in water at a pH of 7 under identical ionic strength gave spherical micelles ranging in size from 9 to 30 nm. Subsequent calculations of the PSTY core density, average surface area per PAA arm on the corona-core interface, and the relative stretching of the PAA arms provided insights into the effect of architecture on the self-assembly processes. A particular trend was observed that with increased architectural complexity the hydrodynamic diameter, radius of the core in the dry state and the aggregation number also increased with the exception of the third generation dendrimer. On the basis of these observations, we postulate that thermodynamic factors controlling self-assembly were the entropic penalty of forming PSTY loops in the core counterbalanced by the reduction in repulsive forces through chain stretching. This results in a greater number of aggregating unimers and consequently larger micelle sizes. The junction points within the architecture also play an important role in controlling the self-assembly process. The G3 dendrimer showed results contradictory to the aforementioned trend. We believe that the self-assembly process of this architecture was dominated by the increased attractive forces due to stretching of the PSTY core chains to form a more compact core. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6292-6303, 2009
Keyword block copolymers
radical polymerization
self-assembly
LIVING RADICAL POLYMERIZATION
SELECTIVE DEGRADABLE LINKAGES
DYNAMICS SIMULATION APPROACH
AB LINEAR DIBLOCK
BLOCK-COPOLYMERS
MICELLIZATION BEHAVIOR
CLICK CHEMISTRY
SUPRAMOLECULAR DENDRIMERS
AGGREGATION PHENOMENA
MICELLAR PROPERTIES
Q-Index Code C1
Q-Index Status Confirmed Code

 
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Created: Sun, 29 Nov 2009, 00:02:36 EST