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Conventional theories of weak polyelectrolytes are either computationally prohibitive to account for the multidimensional inhomogeneity of polymer ionization in a liquid environment or oversimplistic in describing the coupling effects of ion-explicit electrostatic interactions and long-range intrachain correlations. To bridge this gap, we implement the Ising density functional theory (iDFT) for ionizable polymer systems using the single-chain-in-mean-field algorithm. The single-chain-in-iDFT (sc-iDFT) shows significant improvements over conventional mean-field methods in describing segment-level dissociation equilibrium, specific ion effects, and long-range intrachain correlations. With an explicit consideration of the fluctuations of polymer configurations and the position-dependent ionization of individual polymer segments, sc-iDFT provides a faithful description of the structure and thermodynamic properties of inhomogeneous weak polyelectrolyte systems across multiple length scales.
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Thermodynamic non-ideality in charge regulation of weak polyelectrolytes
Polymer ionization differs from that for their monomeric counterparts due to intramolecular correlations. Such effects are conventionally described in terms of the site-binding model that accounts for short-range interactions between neighboring sites. With an apparent equilibrium constant for each ionizable group and the nearest-neighbor energy as adjustable parameters, the site-binding method is useful to correlate experimental titration curves when the site–site interactions are insignificant at long ranges. This work aims to describe the electrostatic behavior of weak polyelectrolytes in aqueous solutions on the basis of the intrinsic equilibrium constants of the individual ionizable groups and solution conditions underlying the thermodynamic non-ideality. A molecular thermodynamic model is proposed for the protonation of weak polyelectrolytes by incorporating classical density functional theory into the site-binding model to account for the effects of the local ionic environment on both inter-chain and intra-chain correlations. By an extensive comparison of theoretical predictions with experimental titration curves, we demonstrate that the thermodynamic model is able to quantify the ionization behavior of weak polyelectrolytes over a broad range of molecular architectures and solution conditions.
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- Award ID(s):
- 1940118
- PAR ID:
- 10337802
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 17
- Issue:
- 40
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 9221 to 9234
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1SM00848J
