Polyelectrolyte complex coacervates of homologous (co)polyelectrolytes with a near-ideally random distribution of a charged and neutral ethylene oxide comonomer were synthesized. The unique platform provided by these building blocks enabled an investigation of the phase behavior across charge fractions 0.10 ≤ f ≤ 1.0. Experimental phase diagrams for f = 0.30–1.0 were obtained from thermogravimetric analysis of complex and supernatant phases and contrasted with molecular dynamics simulations and theoretical scaling laws. At intermediate to high f , a dependence of polymer weight fraction in the salt-free coacervate phase ( w P,c ) of w P,c ∼ f 0.37±0.01 was extracted; this trend was in good agreement with accompanying simulation predictions. Below f = 0.50, w P,c was found to decrease more dramatically, qualitatively in line with theory and simulations predicting an exponent of 2/3 at f ≤ 0.25. Preferential salt partitioning to either coacervate or supernatant was found to be dictated by the chemistry of the constituent (co)polyelectrolytes.
The utilization of chemical sequence control in polymeric materials is key to enabling material design on par with biomacromolecular systems. One important avenue for scalable sequence-controlled polymers leverages the random copolymerization of distinct monomers, with the statistical distribution of the monomeric sequence arising from reaction kinetics following a first-order Markov process. Here we utilize the framework of the random phase approximation (RPA) to develop a theory for the phase behavior of symmetric polyelectrolyte coacervates whose chemical sequences are dictated by simple statistical distributions. We find that a high charge “blockiness” within the random sequences favors the formation of denser and more salt-resistant coacervates while simultaneously increasing the width of the two-phase region. We trace these physical effects to the increased cooperativity of Coulomb interactions that results from increased charge blockiness in oppositely charged polyelectrolytes.
Considerable interest in the dynamics and rheology of polyelectrolyte complex coacervates has been motivated by their industrial application as viscosity modifiers. A central question is the extent to which classical Rouse and reptation models can be applied to systems where electrostatic interactions play a critical role on the thermodynamics. By relying on molecular simulations, we present a direct analysis of the crossover from Rouse to reptation dynamics in salt-free complex coacervates as a function of chain length. This crossover shifts to shorter chain lengths as electrostatic interactions become stronger, which corresponds to the formation of denser coacervates. To distinguish the roles of Coulomb interactions and density, we compare the dynamics of coacervates to those of neutral, semidilute solutions at the same density. Both systems exhibit a universal dynamical behavior in the connectivity-dominated (subdiffusion and normal diffusion) regimes, but the monomer relaxation time in coacervates is much longer and increases with increasing Bjerrum length. This is similar to the cage effect observed in glass-forming polymers, but the local dynamical slowdown is caused here by strong Coulomb attractions (ion pairing) between oppositely charged monomers. Our findings provide a microscopic framework for the quantitative understanding of coacervate dynamics and rheology.
We have directly observed the in situ self-assembly kinetics of polyelectrolyte complex (PEC) micelles by synchrotron time-resolved small-angle X-ray scattering, equipped with a stopped-flow device that provides millisecond temporal resolution. A synthesized neutral-charged diblock polycation and homopolyanion that we have previously investigated as a model chargematched, core−shell micelle system were selected for this work. The initial micellization of the oppositely charged polyelectrolytes was completed within the dead time of mixing of 100 ms, followed by micelle growth and equilibration up to several seconds. By combining the structural evolution of the radius of gyration (R g ) with complementary molecular dynamics simulations, we show how the self-assemblies evolve incrementally in size over time through a two-step kinetic process: first, oppositely charged polyelectrolyte chains pair to form nascent aggregates that immediately assemble into spherical micelles, and second, these PEC micelles grow into larger micellar entities. This work has determined one possible kinetic pathway for the initial formation of PEC micelles, which provides useful physical insights for increasing fundamental understanding self-assembly dynamics, driven by polyelectrolyte complexation that occurs on ultrafast time scales.
Monomer sequences in statistical (co)polyelectrolytes can be used to tune complex coacervation, including density and structure of the polymer-rich phase.
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