Abstract
There has been significant interest recently in the development of materials that utilize the kinetic properties of self-associating groups, which can be tuned to manipulate dynamics and control mechanical, optical, and rheological properties. Here we describe the single-chain behavior of self-associating polymers in solution, using results from both simulation and theory. We use Brownian dynamics simulations with monomers that can reversibly associate using Bell model-based reaction kinetics. A straightforward two-state model is considered, and associations are exclusive; however, generalizations beyond these behaviors are briefly considered in the theory. We demonstrate that, even for a Θ-polymer, the inclusion of self-associations can drive the polymer into an equilibrium structure that resembles a collapsed polymer globule. The dynamic behavior of these polymers exhibits two regimes, with Rouse-dominated time scales when binding reactions have low energetic barriers and binder-dominated time scales when binding reactions have large energetic barriers. These results have implications in a diverse array of applications ranging from supramolecular chemistry to stimuli responsive materials to biological polymer dynamics.
Original language | English (US) |
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Pages (from-to) | 6962-6971 |
Number of pages | 10 |
Journal | Macromolecules |
Volume | 44 |
Issue number | 17 |
DOIs | |
State | Published - Sep 13 2011 |
Externally published | Yes |
ASJC Scopus subject areas
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry