TY - JOUR
T1 - Complex coacervation of statistical polyelectrolytes
T2 - Role of monomer sequences and formation of inhomogeneous coacervates
AU - Yu, Boyuan
AU - Rumyantsev, Artem M.
AU - Jackson, Nicholas E.
AU - Liang, Heyi
AU - Ting, Jeffrey M.
AU - Meng, Siqi
AU - Tirrell, Matthew V.
AU - De Pablo, Juan J.
N1 - Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2021/10
Y1 - 2021/10
N2 - Advances in synthetic chemistry have led to greater control over the sequence of polymeric materials, and the ability to create patterns whose complexity is reminiscent of that of biological macromolecules. In random copolymers synthesized via statistical copolymerization, the sequence follows a first-order Markov chain process governed by the underlying reactivity ratios. In this work, theory and simulations are combined to study the role of sequence in the complex coacervation of oppositely charged random (co)polyelectrolytes, i.e. copolymers comprising cationic/anionic and neutral monomers. It is found that charged monomers enhance the proclivity towards complex coacervation, and enhance the coacervates' stability upon addition of salt. This result is general, and holds for both good and poor solvents, despite the different ("closed"and "open") shapes of the respective coacervation binodals. For high charge blockiness, simulations reveal the formation of microphase separated coacervates consisting of domains rich in ionic or neutral monomers. The transition from homogeneous to locally segregated coacervates leads to a non-monotonic dependence of the density on charge blockiness. Our results provide a comprehensive framework to understand and interpret the effects of sequence on complex coacervation, and for rational design of coacervate-based materials.
AB - Advances in synthetic chemistry have led to greater control over the sequence of polymeric materials, and the ability to create patterns whose complexity is reminiscent of that of biological macromolecules. In random copolymers synthesized via statistical copolymerization, the sequence follows a first-order Markov chain process governed by the underlying reactivity ratios. In this work, theory and simulations are combined to study the role of sequence in the complex coacervation of oppositely charged random (co)polyelectrolytes, i.e. copolymers comprising cationic/anionic and neutral monomers. It is found that charged monomers enhance the proclivity towards complex coacervation, and enhance the coacervates' stability upon addition of salt. This result is general, and holds for both good and poor solvents, despite the different ("closed"and "open") shapes of the respective coacervation binodals. For high charge blockiness, simulations reveal the formation of microphase separated coacervates consisting of domains rich in ionic or neutral monomers. The transition from homogeneous to locally segregated coacervates leads to a non-monotonic dependence of the density on charge blockiness. Our results provide a comprehensive framework to understand and interpret the effects of sequence on complex coacervation, and for rational design of coacervate-based materials.
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U2 - 10.1039/d1me00076d
DO - 10.1039/d1me00076d
M3 - Article
AN - SCOPUS:85116715743
SN - 2058-9689
VL - 6
SP - 790
EP - 804
JO - Molecular Systems Design and Engineering
JF - Molecular Systems Design and Engineering
IS - 10
ER -