Molecules that contain both water-friendly and water-unfriendly segments play a central role in a variety of biological and artificial processes, and are in widespread use as emulsifiers, detergents, drug delivery vehicles, templates for nanomaterials and oil recovery agents. The research in this award will develop and explore a new class of giant surfactant molecules with a highly adjustable brush-like structure. Spontaneous assembly of these molecular building blocks in water will be pursued as a means of rapidly generating materials with a diverse set of properties. The proposed research activities will advance the current understanding of molecular self-assembly, and provide access to high-value nanomaterials for potential utilization in energy- and health-related applications. The scientific goals of this research project will be integrated with broader outreach and educational initiatives, aimed at improving pre-K-12 and undergraduate STEM education, and developing a globally competitive STEM workforce. A newly organized Western New York STEM Forum will be used as a platform for teacher professional development, while undergraduate chemistry curricula will be enhanced via polymer-based laboratory modules.
This project aims to develop new bottlebrush-based macromolecular surfactants and understand their aqueous phase behavior. The research supported by this grant will focus on (1) preparation of amphiphilic bottlebrush block copolymers, (2) micelle formation in dilute solutions, (3) lyotropic assembly, and (4) fabrication of nanostructured interfaces and materials by utilizing shape-persistent bottlebrush copolymers as molecular building blocks. The polymers will be synthesized by grafting-from and grafting-through methods to provide surfactants with precise structural and functional control. Ring-opening and controlled radical polymerization techniques will be employed for the synthesis of well-defined copolymers. Self-assembly of bottlebrush surfactants with varying backbone and side chain asymmetries will be investigated in dilute and concentrated aqueous solutions by means of small angle x-ray scattering and cryogenic transmission electron microscopy. Interfacial assembly of the compartmentalized amphiphilic bottlebrush copolymers will be utilized for the preparation of mesoporous particles and membranes. The successful outcome of the proposed research activities will result in phenomenological understanding of the shape-dependent assembly of giant bottlebrush surfactants and the fabrication of previously unattainable nanostructured materials for a variety of applications. The experimental results will be augmented by collaborative computational and modeling efforts.
