Dopamine-melanin (DM or "polydopamine") can be deposited on virtually any substrate from solution through autoxidation of dopamine. The versatility of this process has allowed surface-mediated assembly of DM for a wide variety of functional coatings. Here we report the impact of well-defined surface chemistries on the nucleation and growth of such films. DM was deposited on silicon dioxide (SiO2) and SiO2 substrates modified with self-assembled monolayers (SAMs) bearing octadecyl (C18), phenethyl, and aminopropyl functional groups. Atomic force microscopy revealed three-dimensional islands whose areal density and surface coverage are lowest on bare SiO2 substrates and highest on the neutral aromatic and aliphatic substrates. Increasing the pH of the solution from 8.2 to 10 dissociates catechol moieties in DM and inhibits adsorption on negatively charged SiO2 substrates. The growth rate of DM films on SAM-modified SiO2 is maximized at pH 9.5 and almost completely abolished at pH 10 because of increased DM solubility. The initial rates of DM adsorption were measured using quartz crystal microbalance with dissipation measurements. The initial adsorption rate is proportional to the nucleation density, which increases as the hydrophobicity of the substrate increases. Taken together, these data provide insight into the rates of heterogeneous nucleation and growth of DM on substrates with well-defined chemistries.
