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Communication: Counter-ion solvation and anomalous low-angle scattering in salt-free polyelectrolyte solutions.

ABSTRACT: We investigate the influence of counter-ion solvation on the homogeneity of salt-free polyelectrolyte solutions based on a coarse-grained model that includes an explicit solvent. We show that the solvation of the counter-ions can cause a transformation between a nearly homogeneous to a non-uniform polymer solution, in which there is both a chain clustering and the formation of large charge-free domains, i.e., "voids." The emergence of these heterogeneous structures induced by counter-ion solvation is accompanied by the localization and formation of counter-ion rich domains that are symptomatic of emergent effective long-range attractive interchain interactions.

SUBMITTER: Chremos A

PROVIDER: S-EPMC5839105 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature

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Communication: Counter-ion solvation and anomalous low-angle scattering in salt-free polyelectrolyte solutions.

Chremos Alexandros A Douglas Jack F JF

The Journal of chemical physics 20171201 24

We investigate the influence of counter-ion solvation on the homogeneity of salt-free polyelectrolyte solutions based on a coarse-grained model that includes an explicit solvent. We show that the solvation of the counter-ions can cause a transformation between a nearly homogeneous to a non-uniform polymer solution, in which there is both a chain clustering and the formation of large charge-free domains, i.e., "voids." The emergence of these heterogeneous structures induced by counter-ion solvati ...[more]

PMID: 29289148

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Project description:There has been significant interest in the tendency of highly charged particles having the same charge to form dynamic clusters in solution, but an accepted theoretical framework that can account for this ubiquitous phenomenon has been slow to develop. The theoretical difficulties are especially great for flexible polyelectrolytes due to the additional complex coupling between the polyelectrolyte chain configurations and the spatial distribution of the ionic species in solution. For highly charged polyelectrolytes, this leads to the formation of a diffuse "polarizable" cloud of counter-ions around these polymers, an effect having significant implications for the function of proteins and other natural occurring polyelectrolytes, as emphasized long ago by Kirkwood and co-workers. To investigate this phenomenon, we perform molecular dynamics simulations of a minimal model of polyelectrolyte solutions that includes an explicit solvent and counter-ions, where the relative affinity of the counter-ions and the polymer for the solvent is tunable through the variation of the relative strength of the dispersion interactions of the polymer and ions. In particular, we find that these dispersion interactions can greatly influence the nature of the association between the polyelectrolyte chains under salt-free conditions. We calculate static and dynamic correlation functions to quantify the equilibrium structure and dynamics of these complex liquids. Based on our coarse-grained model of polyelectrolyte solutions, we identify conditions in which three distinct types of polyelectrolyte association arise. We rationalize these types of polyelectrolyte association based on the impact of the selective solvent affinity on the charge distribution and polymer solvation in these solutions. Our findings demonstrate the essential role of the solvent in the description of the polyelectrolyte solutions, as well as providing a guideline for the development of a more predictive theory of the properties of the thermodynamic and transport properties of these complex fluids.

Dataset Information

Communication: Counter-ion solvation and anomalous low-angle scattering in salt-free polyelectrolyte solutions.

Publications

Communication: Counter-ion solvation and anomalous low-angle scattering in salt-free polyelectrolyte solutions.

Similar Datasets

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