Coupling of conformational and ionization equilibria in linear poly(ethylenimine): a study based on the site binding/rotational isomeric state (SBRIS) model

Literature Information

Publication Date 2013-12-18
DOI 10.1039/C3CP54211D
Impact Factor 3.676
Authors

J. L. Garcés, S. Madurga, M. Borkovec


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Abstract

The conformational and ionization properties of linear poly(ethylenimine) are studied by combining the site binding model (SB) with the rotational isomeric state (RIS) model, developed by Flory to calculate the conformational properties of neutral linear molecules. The resulting approach (the SBRIS model) is used to rationalise the experimental poly(ethylenimine) titration curves. By fitting the experimental macroconstants, conformational and binding parameters are obtained. The obtained values are consistent with previous binding and structural information. The emergence of triplet interaction between protonated sites is explained as a natural consequence of the coupling between binding and conformational equilibria. When only nearest neighbour interactions are considered, transfer matrix techniques are used in the calculations. In order to account for excluded volume and long-range electrostatic interactions, Monte Carlo simulations are performed. The results indicate that at high ionic strengths, long-range interactions have a very limited impact on the titration curves. However, for long chains, they have a significant influence on the radius of gyration.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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