Abstract
Biomacromolecules rely on the precise placement of monomers to encode information for structure, function, and physiology. Efforts to emulate this complexity via the synthetic control of chemical sequence in polymers are finding success; however, there is little understanding of how to translate monomer sequence to physical material properties. Here we establish design rules for implementing this sequence-control in materials known as complex coacervates. These materials are formed by the associative phase separation of oppositely charged polyelectrolytes into polyelectrolyte dense (coacervate) and polyelectrolyte dilute (supernatant) phases. We demonstrate that patterns of charges can profoundly affect the charge–charge associations that drive this process. Furthermore, we establish the physical origin of this pattern-dependent interaction: there is a nuanced combination of structural changes in the dense coacervate phase and a 1D confinement of counterions due to patterns along polymers in the supernatant phase.
Highlights
Biomacromolecules rely on the precise placement of monomers to encode information for structure, function, and physiology
Charge interactions differ from short-range interactions, leading to different types of design rules; this difference can be tied to both the long-range nature of electrostatic interactions, and the complementarity between positive and negative charges suppressing like interactions and promoting partner interactions
We demonstrate that sequence specificity of charged monomers can be used to precisely control the selfassembly and thermodynamics of a class of materials known as complex coacervates[22, 23]
Summary
Biomacromolecules rely on the precise placement of monomers to encode information for structure, function, and physiology Efforts to emulate this complexity via the synthetic control of chemical sequence in polymers are finding success; there is little understanding of how to translate monomer sequence to physical material properties. The continuum of behaviors between block and random co-polymers has been probed in terms of equilibrium properties (e.g., phase behavior[18, 19], compatibilization20) using coarsegrained modeling and theory These works consider portions of a vast sequence parameter space, using monomer sequence correlations (i.e., blockiness)[18, 19], sophisticated machine learning methods[20], or sequence gradients[21]. We experimentally and computationally demonstrate the effects of charge patterning, and establish the physical picture and design rules necessary to show why charge patterning has such a profound effect on coacervate phase behavior
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