Interplay between self-assembly and phase separation in a polymer-complex model

Abstract

We present a theoretical model for predicting the phase behavior of polymer solutions in which phase separation competes with oligomerization. Specifically, we consider scenarios in which the assembly of polymer chains into stoichiometric complexes prevents the chains from phase-separating via attractive polymer-polymer interactions. Combining statistical associating fluid theory with a two-state description of self-assembly, we find that this model exhibits rich phase behavior, including re-entrance, and we show how system-specific phase diagrams can be derived graphically. Importantly, we discuss why these phase diagrams can resemble -- and yet are qualitatively distinct from -- phase diagrams of polymer solutions with lower critical solution temperatures.

References in corpus (4)

• Accurate phase diagram of tetravalent DNA nanostars
• Self-assembly in chains, rings and branches: a single component system with two critical points
• Thermodynamic Approach to Phase Coexistence in Ternary Phospholipi-Cholesterol Mixtures
• Reentrant phase behaviour for systems with competition between phase separation and self-assembly

Cited by in corpus (3)

• Competition between self-assembly and phase separation governs high-temperature condensation of a DNA liquid
• Counterion-controlled phase equilibria in a charge-regulated polymer solution
• Cooperation and competition of basepairing and electrostatic interactions in mixtures of DNA nanostars and polylysine