PAMAM-Based Dendrimers with Different Alkyl Chains Self-Assemble on Silica Surfaces: Controllable Layer Structure and...

Amphiphilic poly(amidoamine) (PAMAM) dendrimers are a well-known dendritic family due to their remarkable ability to self-assemble on solid surface. However, the relationship between molecular conformation (or adsorption kinetics) of a self-assembled layer and molecular amphiphilicity of such kind of dendrimer is still lacking, which limits the development of modulating self-assembling structures and surface functionality. With this in mind, we synthesized a series of amphiphilic PAMAM-based dendrimers, denoted as G₁C _n, with different alkyl chains ( n = 8, 12, and 16), and investigated the molecular aggregation on silica surfaces by means of quartz crystal microbalance with dissipation, atomic force microscopy, and contact angle. After rinsing, remaining adsorption amounts of G₁C₁₂ were higher than those of G₁C₈ at high concentrations, suggesting that G₁C₁₂ adlayers were more stable due to the stronger intermolecular hydrophobic interactions, whereas it preferred to adopt the intramolecular hydrophobic interactions for G₁C₁₆, with low adsorption amounts and unstable adlayers. Bilayer-like structures were inferred in G₁C₈ and G₁C₁₂ adlayers with loose conformation, whereas monolayer structures were likely to exist in the sparse adsorption film of G₁C₁₆. Our results provided more detailed understanding of the effect of molecular structure on the self-assembled structures of amphiphilic dendrimers on solid surfaces, shedding light on the controlled microstructure and wettability of functional surface by modulating the length of hydrophobic chains of dendrimers and a potential application of dendrimer-substrate combinations.