Impact of Polydopamine Nanoparticle Surface Pattern and Roughness on Interactions with Poly(ethylene glycol) in Aqueous Solution: A Multiscale Modeling and Simulation Study.

A significant research effort in the past few years has been devoted to engineering synthetic mimics of naturally occurring eumelanin. One such effort has involved the assembly of oligomers of 5,6-dihydroxyindole (DHI), a synthetic precursor of polydopamine (PDA), into melanin-mimicking nanoparticles for use in a variety of applications with desired optical, photonic, thermal, and electrical properties. In many of these applications, the PDA nanoparticles are mixed with other polymers or oligomers, thus motivating this specific study to understand how the surface characteristics of the assembled PDA-nanoparticles affect their interaction with poly(ethylene glycol) (PEG) chains in aqueous solution. We use molecular dynamics (MD) simulations to study the interaction of linear 20-mer PEG chains with different PDA-nanoparticles assembled using four types of oligomers of 5,6-DHI: two isomers of 5,6-DHI 2-mers with the monomers bonding either at the 2-2' position (A-type isomer) or 7-7' position (B-type isomer), denoted as A:2-mer and B:2-mer, respectively, and a 4-mer and an 8-mer of B-type chemistry denoted as B:4-mer and B:8-mer, respectively. Using explicit-solvent atomistic MD simulations, we find that PDA-nanoparticle surfaces assembled from B:8-mer exhibit smaller density fluctuations of water molecules and, as a result, are relatively more hydrophilic than the PDA-nanoparticle surfaces assembled from A:2-mer, B:2-mer, and B:4-mer. The surface composition of PDA-nanoparticles assembled from A:2-mer contains relatively fewer hydroxyl (-OH) groups compared to PDA-nanoparticles assembled from a B:2-mer, B:4-mer, or B:8-mer, yet the sample of PEG chains show more collapsed and adsorbed conformations on A:2-mer nanoparticles' surface. To explain the atomistically observed behavior of PEG chains on the nanoparticles' surfaces, we use coarse-grained (CG) MD simulations and explain the roles of the pattern formed by the attractive sites (e.g.,-OH groups) exposed on the surface and the roughness of the surface on interactions with a genric PEG-like copolymer chain. By comparing atomistic and CG MD simulation results, we confirm that the -OH groups' pattern on the surface of the PDA-nanoparticle assembled from A:2-mer is patchier than the random or string-like patterns on the PDA-nanoparticle assembled from B:2-mer, B:4-mer, or B:8-mer, and it is this -OH groups' surface pattern that dictates the PEG chain conformations and adsorption on the PDA-nanoparticle surface. Overall, these results guide the design of chemically and physically heterogeneous nanoparticle surfaces for the desired polymer interaction and conformations.