Inducing pH control over the critical micelle concentration of zwitterionic surfactants via polyacids adsorption: Effect of chain length and structure

Abstract

Hypothesis: The critical concentration above which micelles form from zwitterionic surfactant solutions and their thermodynamic stability is affected by the interaction with weak Brønsted polyacid chains (A_n) via the formation of charged hydrogen bonds between the latter and anionic moieties.

Experiments: The interaction between zwitterionic micelles and polyacids capable of forming hydrogen bonds, and its dependence on the environmental pH and polymer structure, has been studied with constant-pH simulations and a restricted primitive model for all electrolytes.

Findings: At low pH, the formation of polyacid/micelle complexes is witnessed independently of the polymer size or structure, so that the concentration above which micelles form is substantially decreased compared to polyacid-free cases. Upon rising pH, polymer desorption takes place within a narrow range of pH values, its location markedly depending on the size and structure of polyacids, and on the relative disposition between headgroup charged moieties. Thus, the desorption onset for long linear polyacids (A₆₀) interacting with sulphobetainic headgroups is roughly two pH units higher than for six decameric chains (6A₁₀) adsorbed onto micelles bearing phosphorylcholinic headgroups. This effect, together with the preferential desorption of chain ends at intermediate pH, may be exploited for drug delivery purposes or building advanced metamaterials.

Keywords: Micelles; Polyacids; Polyelectrolyte complexes; Zwitterionic surfactants; pH-responsive systems.