Molecular design of self-coacervation phenomena in block polyampholytes.

Abstract:

:Coacervation is a common phenomenon in natural polymers and has been applied to synthetic materials systems for coatings, adhesives, and encapsulants. Single-component coacervates are formed when block polyampholytes exhibit self-coacervation, phase separating into a dense liquid coacervate phase rich in the polyampholyte coexisting with a dilute supernatant phase, a process implicated in the liquid-liquid phase separation of intrinsically disordered proteins. Using fully fluctuating field-theoretic simulations using complex Langevin sampling and complementary molecular-dynamics simulations, we develop molecular design principles to connect the sequenced charge pattern of a polyampholyte with its self-coacervation behavior in solution. In particular, the lengthscale of charged blocks and number of connections between oppositely charged blocks are shown to have a dramatic effect on the tendency to phase separate and on the accessible chain conformations. The field and particle-based simulation results are compared with analytical predictions from the random phase approximation (RPA) and postulated scaling relationships. The qualitative trends are mostly captured by the RPA, but the approximation fails catastrophically at low concentration.

authors

Danielsen SPO,McCarty J,Shea JE,Delaney KT,Fredrickson GH

doi

10.1073/pnas.1900435116

subject

Has Abstract

pub_date

2019-04-23 00:00:00

pages

8224-8232

issue

17

eissn

0027-8424

issn

1091-6490

pii

1900435116

journal_volume

116

pub_type

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