Bundlemer-templated Block Copolymers

University Of Delaware, Newark DE

Investigators

Abstract

With the support of the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Professors Christopher J. Kloxin and Darrin J. Pochan at the University of Delaware will synthesize innovative polymeric materials using biologically inspired nanoparticles. Traditional block copolymers, composed of two or more chemically bonded polymers, have significantly impacted polymer science and are used in a wide range of applications, from adhesives to biomedical implants. This research uses biologically derived nanoparticles called bundlemers to initiate and guide polymer synthesis, creating a new class of block copolymers. The templated display of polymers can not only mimic traditional block copolymer materials but also allows for the creation of entirely new materials through programmed materials assembly. The modular nature of bundlemer-templated block copolymers allows for the simple creation of more sophisticated and advanced materials. These research activities will offer undergraduate and graduate students invaluable educational experiences in polymer and materials chemistry. Additionally, the research team will further enhance their impact by engaging with K-12 students and the broader community through various outreach activities and programs. The research team will synthesize bundlemer-templated block copolymers, leveraging the unique feature of bundlemers to precisely position molecular species and enabling new complex morphologies. The bundlemer-forming peptides will be synthesized with atom-transfer radical polymerization (ATRP) initiator sites that will ultimately reside at predetermined locations along the bundlemer periphery. After surface-initiated ATRP, unique polymer interactions will be displayed in specific directions from the bundlemer surface. Polymers will be initiated at designated sites to study the effect of initiator site location. Characterization of polymer grafts will be achieved through selective cleavage. Site locations and polymer types will be examined to assess their impact on the polymerization kinetics and molar mass distribution. Using ‘click’ chemical conjugation, the modular nature of the bundlemer-templated copolymers will be exploited to create new bottlebrush polymer-like structures. Modulating polymer interactions along the rod-like polybundlemer structure enables unique patterned interactions between these rod-like assemblies. A range of polymerization conditions and polymer types will be explored, and structural verification conducted using light scattering, film-cast and cryogenic transmission electron microscopy, and small angle neutron and x-ray scattering. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.