From complexation of oppositely charged polyelectrolytes to supramolecular bottlebrushes and gels.
July 22-25, 2018
We develop a scaling model of coacervates formed by oppositely charged polyelectrolytes. The intramolecular electrostatic interactions in dilute polyanion or polycation solutions are characterized by the so-called electrostatic blobs, D- or D+ respectively. Polyelectrolyte sections of electrostatic blob size repel neighboring sections of the same chain with electrostatic energy on the order of thermal energy kT. Conformations of polyanion or polycation chains in their respective dilute solutions with no added salt can be described as stretched arrays of their corresponding electrostatic blobs of size D- or D+. The structure of a coacervate formed upon mixing polyanion and polycation solutions depends on the electrostatic attraction between oppositely charged polyelectrolytes balanced by the short-range repulsion. In the symmetric case with D- = D+ = De the coacervate is a dense packing of these electrostatic blobs with neighboring oppositely charged blobs of size De attracting each other with energy on order kT. This attraction is stabilized by short-range non-electrostatic repulsion with energy on the same order kT between all chain sections of size De.
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Michael Rubinstein, Qi Liao, and Sergey Panyukov, "From complexation of oppositely charged polyelectrolytes to supramolecular bottlebrushes and gels." in "Advances in Cosmetic Formulation Design", ECI Symposium Series, (2018). http://dc.engconfintl.org/cosmetic/41