Molecular Insight into the Effect of Polymer Topology on Wettability of Block Copolymers: The Case of Amphiphilic Polyurethanes.

The microstructure design of multiblock copolymers is essential for achieving desired interfacial properties in submerged applications. Two major design factors are the chemical composition and polymer topology. Despite a clear relationship between chemical composition and wetting, the effect of polymer topology (i.e., linear vs cross-linked polymers) is not very clear. Thus, in this study, we shed light on the molecular origins of polymer topology on the wetting behavior. To this end, we synthesized linear and three-dimensional (3D) cross-linked network topologies of poly(ethylene glycol) (PEG)-modified polycarbonate polyurethanes with the same amount of hydrophilic PEG groups on the surface (confirmed by X-ray photoelectron spectroscopy (XPS)) and studied the wetting mechanisms through water contact angle (WCA), atomic force microscopy (AFM), and molecular dynamics (MD) simulations. The linear topology exhibited superhydrophilic behavior, while the WCA of the cross-linked polymer was around 50°. AFM analysis (performed on dry and wet samples) suggests that PEG migration toward the interface is the dominant factor. MD simulations confirm the AFM results and unravel the mechanisms: the higher flexibility of PEG in linear topology results in a greater PEG migration to the interface and formation of a thicker interfacial layer (i.e., twice as thick as the cross-linked polymers). Accordingly, water diffusion into the interfacial layer was greater in the case of the linear polymer, leading to better screening of the underneath hydrophobic (polycarbonate) segments.

PolySMart: a general coarse-grained molecular dynamics polymerization scheme.

The development of simulation methods to study the structure and dynamics of a macroscopically sized piece of polymer material is important as such methods can elucidate structure-property relationships. Several methods have been reported to construct initial structures for homo- and co-polymers; however, most of them are only useful for short linear polymers since one needs to pack and equilibrate the far-from-equilibrium initial structures, which is a tedious task for long or hyperbranched polymers and unfeasible for polymer networks. In this method article, we present PolySMart, i.e., an open-source python package, which can effectively produce fully equilibrated homo- and hetero-polymer melts and solutions with no limitation on the polymer topology and size, at a coarse-grained resolution and through a bottom-up approach. This python package is also capable of exploring the polymerization kinetics through its reactive scheme in realistic conditions so that it can model the multiple co-occurring polymerization reactions (with different reaction rates) as well as consecutive polymerizations under stoichiometric and non-stoichiometric conditions. Thus, the equilibrated polymer models are generated through correct polymerization kinetics. A benchmark and verification of the performance of the program for several realistic cases, i.e., for homo-polymers, co-polymers, and crosslinked networks, is given. We further discuss the capability of the program to contribute to the discovery and design of new polymer materials.

Supramolecular Engineering of Alkylated, Fluorinated, and Mixed Amphiphiles.

The rational design of perfluorinated amphiphiles to control the supramolecular aggregation in an aqueous medium is still a key challenge for the engineering of supramolecular architectures. Here, the synthesis and physical properties of six novel non-ionic amphiphiles are presented. The effect of mixed alkylated and perfluorinated segments in a single amphiphile is also studied and compared with only alkylated and perfluorinated units. To explore their morphological behavior in an aqueous medium, dynamic light scattering (DLS) and cryogenic transmission electron microscopy/electron microscopy (cryo-TEM/EM) measurements are used. The assembly mechanisms with theoretical investigations are further confirmed, using the Martini model to perform large-scale coarse-grained molecular dynamics simulations. These novel synthesized amphiphiles offer a greater and more systematic understanding of how perfluorinated systems assemble in an aqueous medium and suggest new directions for rational designing of new amphiphilic systems and interpreting their assembly process.