Design of Soft Material Surfaces with Rationally Tuned Water Diffusivity.

Water structure and dynamics can be key modulators of adsorption, separations, and reactions at soft material interfaces, but systematically tuning water environments in an aqueous, accessible, and functionalizable material platform has been elusive. This work leverages variations in excluded volume to control and measure water diffusivity as a function of position within polymeric micelles using Overhauser dynamic nuclear polarization spectroscopy. Specifically, a versatile materials platform consisting of sequence-defined polypeptoids simultaneously offers a route to controlling the functional group position and a unique opportunity to generate a water diffusivity gradient extending away from the polymer micelle core. These results demonstrate an avenue not only to rationally design the chemical and structural properties of polymer surfaces but also to design and tune the local water dynamics that, in turn, can adjust the local activity for solutes.

Sequence Modulates Polypeptoid Hydration Water Structure and Dynamics.

We use molecular dynamics simulations to investigate the effect of polypeptoid sequence on the structure and dynamics of its hydration waters. Polypeptoids provide an excellent platform to study small-molecule hydration in disordered polymers, as they can be precisely synthesized with a variety of sidechain chemistries. We examine water behavior near a set of peptoid oligomers in which the number and placement of nonpolar versus polar sidechains are systematically varied. To do this, we leverage a new computational workflow enabling accurate sampling of polypeptoid conformations. We find that the hydration waters are less dense, are more tetrahedral, and have slower dynamics compared to bulk water. The magnitude of these shifts increases with the number of nonpolar groups. We also find that shifts in the water structure and dynamics are strongly correlated, suggesting that experimental insight into the dynamics of hydration water obtained by Overhauser dynamic nuclear polarization (ODNP) also contains information about water structural properties. We then demonstrate the ability of ODNP to probe site-specific dynamics of hydration water near these model peptoid systems.

Effects of Amphiphilic Polypeptoid Side Chains on Polymer Surface Chemistry and Hydrophilicity.

Polymers are commonly used in applications that require long-term exposure to water and aqueous mixtures, serving as water purification membranes, marine antifouling coatings, and medical implants, among many other applications. Because polymer surfaces restructure in response to the surrounding environment, in situ characterization is crucial for providing an accurate understanding of the surface chemistry under conditions of use. To investigate the effects of surface-active side chains on polymer surface chemistry and resultant interactions with interfacial water (i.e., water sorption), we present synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) studies performed on poly(ethylene oxide) (PEO)- and poly(dimethylsiloxane) (PDMS)-based polymer surfaces modified with amphiphilic polypeptoid side chains, previously demonstrated to be efficacious in marine fouling prevention and removal. The polymer backbone and environmental conditions were found to affect polypeptoid surface presentation: due to the surface segregation of its fluorinated polypeptoid monomers under vacuum, the PEO-peptoid copolymer showed significant polypeptoid content in both vacuum and hydrated conditions, while the modified PDMS-based copolymer showed increased polypeptoid content only in hydrated conditions due to the hydrophilicity of the ether monomers and polypeptoid backbone. Polypeptoids were found to bind approximately 2.8 water molecules per monomer unit in both copolymers, and the PEO-peptoid surface showed substantial water sorption that suggests a surface with a more diffuse water/polymer interface. This work implies that side chains are ideal for tuning water affinity without altering the base polymer composition, provided that surface-driving groups are present to ensure activity at the interface. These types of systematic modifications will generate novel polymers that maximize bound interfacial water and can deliver surface-active groups to the surface to improve the effectiveness of polymer materials.

Where Biology and Traditional Polymers Meet: The Potential of Associating Sequence-Defined Polymers for Materials Science.

Polymers with precisely defined monomeric sequences present an exquisite tool for controlling material properties by harnessing both the robustness of synthetic polymers and the ability to tailor the inter- and intramolecular interactions so crucial to many biological materials. While polymer scientists traditionally synthesized and studied the physics of long molecules best described by their statistical nature, many biological polymers derive their highly tailored functions from precisely controlled sequences. Therefore, significant effort has been applied toward developing new methods of synthesizing, characterizing, and understanding the physics of non-natural sequence-defined polymers. This perspective considers the synergistic advantages that can be achieved via tailoring both precise sequence control and attributes of traditional polymers in a single system. Here, we focus on the potential of sequence-defined polymers in highly associating systems, with a focus on the unique properties, such as enhanced proton conductivity, that can be attained by incorporating sequence. In particular, we examine these materials as key model systems for studying previously unresolvable questions in polymer physics including the role of chain shape near interfaces and how to tailor compatibilization between dissimilar polymer blocks. Finally, we discuss the critical challenges-in particular, truly scalable synthetic approaches, characterization and modeling tools, and robust control and understanding of assembly pathways-that must be overcome for sequence-defined polymers to attain their potential and achieve ubiquity.