The Supramolecular Association of Polyelectrolytes to Complementary Charged Surfactants and Protein Assemblies

Abstract

Cohesion matters! The correlation between the conformational rigidity of the polyelectrolyte and the size and stability of the globular assembly is discussed in this review article. Some examples of models for the association of polyelectrolytes to globular assemblies are shown here.Supramolecular complexes of strong polyelectrolytes and oppositely charged ionic micelles or protein assemblies derive their main stabilization from electrostatic interactions that include the counterion condensation/release mechanism and from hydrophobic interactions distributed along apolar sections of the components. The predicted and the experimental behavior of selected complexes differing in the flexibility of the polyelectrolyte and in the cohesion of the complementary assembly is reviewed and analyzed. Depending upon the rigidity of the polyelectrolyte, globular surfactant clusters persist in the final structure or are transformed into elongated assemblies. On the other hand, even the rather rigid DNA molecule is forced to bend by strongly associated cationic protein complexes such as the histone octamers. A general framework should allow the prediction of these structures in terms of the interplay between the persistence length of the polyelectrolyte and the association constant of the protein or the surfactant assembly.

A supramolecular polymerisation model for the structurisation of DNA–lipid complexes

“…The above model, originally suggested by the author [1], has received experimental and theoretical verification [2,[7][8][9][10][11][12]. Cases in which the cohesion *Email: cifjepa@duke.edu of the complementary assembly has prevented its dissociation were considered by Perico and coworkers [14,15].…”

“…The supramolecular organisation of complexes formed by linear polyelectrolytes and complementarily charged surfactants, micelles and protein assemblies has been the subject of extensive investigation [1][2][3][4][5][6][7][8][9][10][11][12]. An important parameter controlling the structure of the complexes has been found to be the competition between the conformational flexibility of the polyelectrolyte and the cohesion of the complementary moiety [11,12].…”

“…The hydrophobic interaction of the aliphatic tails of the surfactant was preserved by interdigitation of a number of DNA-surfactant units, resulting in cylindrical (hexagonal) clusters (cf. the scheme shown in Figure 1) [1,[7][8][9][10][11][12].…”

“…An important parameter controlling the structure of the complexes has been found to be the competition between the conformational flexibility of the polyelectrolyte and the cohesion of the complementary moiety [11,12]. Micelles formed by surfactants having single aliphatic chains with large header group areas have been considered [13].…”

Coarse-grained molecular dynamics simulation of self-assembly of polyacrylamide and sodium dodecylsulfate in aqueous solution

“…These configurations are extensively used in a wide range of industrial fields including detergents, paints, coatings, cosmetics, pharmaceuticals, and tertiary oil recovery [2][3][4][5]. Therefore, intensive efforts have been sent to investigate organized aggregates of polymer and surfactants as well as the interactions between them.…”