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Polymers 2018, 10(12), 1331; https://doi.org/10.3390/polym10121331

Separation and Characterization of Highly Charged Polyelectrolytes Using Free-Solution Capillary Electrophoresis

Institut des Biomolécules Max Mousseron, University of Montpellier, CNRS, ENSCM, 34095 Montpellier, France
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Received: 26 October 2018 / Revised: 26 November 2018 / Accepted: 27 November 2018 / Published: 2 December 2018
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Abstract

The characterization of statistical copolymers of various charge densities remains an important and challenging analytical issue. Indeed, the polyelectrolyte (PE) effective electrophoretic mobility tends to level off above a certain charge density, due to the occurrence of Manning counterion condensation. Surprisingly, we demonstrate in this work that it is possible to get highly resolutive separations of charged PE using free-solution capillary electrophoresis, even above the critical value predicted by the Manning counterion condensation theory. Full separation of nine statistical poly(acrylamide-co-2-acrylamido-2-methylpropanesulfonate) polymers of different charge densities varying between 3% and 100% was obtained by adjusting the ionic strength of the background electrolyte (BGE) in counter electroosmotic mode. Distributions of the chemical charge density could be obtained for the nine PE samples, showing a strong asymmetry of the distribution for the highest-charged PE. This asymmetry can be explained by the different reactivity ratios during the copolymerization. To shed more light on the separation mechanism, effective and apparent selectivities were determined by a systematic study and modeling of the electrophoretic mobility dependence according to the ionic strength. It is demonstrated that the increase in resolution with increasing BGE ionic strength is not only due to a closer matching of the electroosmotic flow magnitude with the PE electrophoretic effective mobility, but also to an increase of the dependence of the PE effective mobility according to the charge density. View Full-Text
Keywords: polyelectrolytes; capillary electrophoresis; charge-density distribution; chemical composition; counterion condensation polyelectrolytes; capillary electrophoresis; charge-density distribution; chemical composition; counterion condensation
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Desvignes, I.; Chamieh, J.; Cottet, H. Separation and Characterization of Highly Charged Polyelectrolytes Using Free-Solution Capillary Electrophoresis. Polymers 2018, 10, 1331.

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