Self-Assembly of Lysine-Based Dendritic Surfactants Modeled by the Self-Consistent Field Approach.

Implementing a united atom model, we apply self-consistent field theory to study structure and thermodynamic properties of spherical micelles composed of surfactants that combine an alkyl tail with a charged lysine-based dendritic headgroup. Following experiments, the focus was on dendron surfactants with varying tail length and dendron generations G0, G1, G2. The heads are subject to acetylation modification which reduces the charge and hydrophilicity. We establish a reasonable parameter set which results in semiquantitative agreement with the available experiments. The critical micellization concentration, aggregation number, and micelle size are discussed. The strongly charged dendronic surfactants micelles are stable for generation numbers G0 and G1, for progressively higher ionic strengths. Associates of G2 surfactants are very small and can only be found at extreme surfactant concentration and salt strengths. Micelles of corresponding weaker charged acetylated variants exist up to G2, tolerate significantly lower salt concentrations, but lose the spherical micelle topology for G0 at high ionic strengths.

Persistence length of dendronized polymers: the self-consistent field theory.

We present numerical results for the thermodynamic rigidity and induced persistence length of dendronized polymers with systematically varied topology of their grafts obtained by the Scheutjens-Fleer self-consistent field method. The results were compared to predictions of an analytical mean-field theory. The two approaches have marked different predictions. In particular, the analytical theory predicts that the induced persistence length and the effective segment aspect ratio of dendronized polymers are increasing functions of the degree of branching of their side chains, whereas numerical calculations provide evidence of the opposite dependences. This discrepancy is argued to be due to the ability of side chains to repartition from the compressed to the dilated regions of a curved bottle brush, which is accounted for by the numerical, but not by the analytical method. The difference is most crucial in the light of the expected ability of dendronized polymers to have a liquid crystalline ordering in semi-dilute solutions.