## Abstract The conformational characteristics of polyelectrolytes end‐grafted on two apposing walls are studied. The monovalent and multivalent counterions are explicitly treated. It is found that the polyelectrolyte brushes undergo a collapse transition in the presence of multivalent counterions
Association of a Cylindrical Polyelectrolyte Brush with Tetravalent Counterions
✍ Scribed by Christian Ruthard; Michael Maskos; Hakan Yildiz; Franziska Gröhn
- Publisher
- John Wiley and Sons
- Year
- 2011
- Tongue
- English
- Weight
- 262 KB
- Volume
- 32
- Category
- Article
- ISSN
- 1022-1336
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✦ Synopsis
Abstract
Cylindrical poly(styrene sulfonate) brushes were combined with a tetravalent double‐DABCO based counterion. With increasing addition of counterion, hydrodynamic radius and radius of gyration decrease and AFM reveals a conformation change from wormlike to curled structures. R~g~/R~h~ changes from 1.3 to 0.9. Above charge stoichiometry, brushes become interconnected into finite size assemblies, which are stable in aqueous solution for charge ratios (ratio of the molar concentration of charged counterion groups to the molar concentration of charged monomer units of the polymer brush) 1 < l < 1.2. They are compact and consist of the brushes in curled (bent) conformation, which is in difference to network‐like aggregates from cylindrical poly(styrene sulfonate) brushes with tetravalent porphyrin counterions (Gröhn et al. Macromolecules 2009) and to a wormlike—bent conformation—helix transition found for another brush counterion system (Müller et al. Soft Matter 2009).
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The effect of dimerization between counterions and/or coions on the structure of the three-component primitive model of polyelectrolyte solution is studied using the integral equation technique for associating fluids. The three-component system contains large and highly charged macroions, intermedia