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Calcium mediated polyelectrolyte adsorption on like-charged surfaces.

Martin Turesson¹, Christophe Labbez, André Nonat

¹ICB, UMR 5209 CNRS, Université de Bourgogne, F-21078 Dijon Cedex, France. martin.turesson@u-bourgogne.fr

Langmuir : the ACS Journal of Surfaces and Colloids

|October 14, 2011

Summary

Calcium ions mediate polyelectrolyte adsorption onto charged surfaces, driven by surface overcharging and ion pairing. Simulations reveal adsorption isotherms peak with increasing calcium or polymer concentration, aligning with experimental data.

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Area of Science:

Physical Chemistry
Polymer Science
Surface Science

Background:

Calcium ions play a crucial role in biological and synthetic polyelectrolyte systems.
Understanding polyelectrolyte adsorption is key to controlling material properties and interfacial phenomena.

Purpose of the Study:

To investigate calcium-mediated adsorption of linear and comb polyelectrolytes onto like-charged surfaces.
To quantify ion pairing between polymers and calcium ions using simulations and experimental data.

Main Methods:

Monte Carlo simulations of polyelectrolyte adsorption in a primitive model.
Integration of simulation results with experimental titration and calcium binding data.
Analysis of ion pairing and surface overcharging effects.

Main Results:

Polymer adsorption is driven by surface overcharging with Ca(2+) and ion pairing.
Simulations predict non-Langmuir adsorption isotherms that exhibit a maximum with increasing Ca(2+) or polymer concentration.
Charge-charge correlations explain the observed non-Langmuir behavior.

Conclusions:

Calcium ion concentration and ion pairing significantly influence polyelectrolyte adsorption.
The study provides a quantitative model for calcium-mediated adsorption, consistent with experimental findings.
Charge correlations are essential for understanding complex adsorption isotherms.