Chemically induced supramolecular reorganization of triblock copolymer assemblies: Trapping of intermediate states via a shell-crosslinking methodology
Open Access
- 2 April 2002
- journal article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences of the United States of America
- Vol. 99 (8), 5058-5063
- https://doi.org/10.1073/pnas.052653099
Abstract
The mechanism of morphological phase transitions was studied for rod-shaped supramolecular assemblies comprised of a poly(acrylic acid)-block-poly(methyl acrylate)-block-polystyrene (PAA90-b-PMA80-b-PS100) triblock copolymer in 33% tetrahydrofuran/water after perturbation by reaction with a positively charged water-soluble carbodiimide. Tetrahydrofuran solvation of the hydrophobic core domain provided the dynamic nature required for the rod-to-sphere phase transition to be complete within 30 min. The intermediate morphologies such as fragmenting rods and pearl-necklace structures were trapped kinetically by the subsequent addition of a diamino crosslinking agent, which underwent covalent crosslinking of the shell layer. Alternatively, shell-crosslinked rod-shaped nanostructures with preserved morphology were obtained by the addition of the crosslinking agent before the addition of the carbodiimide, which allowed for the shell crosslinking to be performed at a faster rate than the morphological reorganization. The formation of robust shell-crosslinked nanostructures provides a methodology by which the morphological evolution processes can be observed, and it allows access to otherwise thermodynamically unstable nanostructures.Keywords
This publication has 40 references indexed in Scilit:
- Comparison of Original and Cross-linked Wormlike Micelles of Poly(ethylene oxide-b-butadiene) in Water: Rheological Properties and Effects of Poly(ethylene oxide) AdditionThe Journal of Physical Chemistry B, 2001
- Synthesis and Self-Assembly of the Organic−Organometallic Diblock Copolymer Poly(isoprene-b-ferrocenylphenylphosphine): Shell Cross-Linking and Coordination Chemistry of Nanospheres with a Polyferrocene CoreMacromolecules, 2001
- Triblock Nanospheres and Their Use as Templates for Inorganic Nanoparticle PreparationChemistry of Materials, 2000
- Morphological Behavior for Micelle from Polystyrene-b-poly[2-(β-d-glucopyranosyloxy)ethyl acrylate] upon Changing the Copolymer ConcentrationChemistry Letters, 2000
- Shell Cross-Linked Nanoparticles Containing Hydrolytically Degradable, Crystalline Core DomainsJournal of the American Chemical Society, 2000
- Kinetics of Micelle Formation with Change of Micelle Shape in a Dilute Solution of Diblock CopolymersMacromolecules, 1998
- Multiple Morphologies Formed from an Amphiphilic ABC Triblock Copolymer in SolutionMacromolecules, 1998
- Morphogenic Effect of Solvent on Crew-Cut Aggregates of Apmphiphilic Diblock CopolymersMacromolecules, 1998
- Three-Layer Micelles of an ABC Block Copolymer: NMR, SANS, and LS Study of a Poly(2−ethylhexyl acrylate)-block-poly(methyl methacrylate)-block-poly(acrylic acid) Copolymer in D2OMacromolecules, 1998
- Kinetic and calorimetric investigations on micelle formation of block copolymers of the poloxamer typeColloids and Surfaces A: Physicochemical and Engineering Aspects, 1995