New advances in cyclopentadiene based materials

University Of California-Santa Barbara, Santa Barbara CA

Investigators

Abstract

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Read de Alaniz of University of California at Santa Barbara will construct polymers capable of self-healing and de-polymerizing using “click” chemistry that leverages non-toxic, metal-free, and inexpensive building blocks. To translate this chemistry for biological utility an aqueous soluble photo-click platform will be developed. The successful realization of this goal will provide the high-resolution spatial control over chemical functionalization required to pattern biomaterials for applications in 3D printing and tissue engineering. Simultaneously this project aims to provide outstanding educational opportunities for students at multiple levels, with a particular focus on those from underrepresented groups. A key broader impact aspect of the proposed research will be the highly interdisciplinary nature of this project that will train and educate the next-generation scientists with broad multidisciplinary skills in organic and polymer synthesis and characterization. Outreach activities leveraging virtual/hybrid educational science talks and lessons for 1st and 2nd grade students will also be developed. The structure will allow young students to meet scientists and provide graduate students an opportunity to communicate their work to a broader audience. While the value of Diels–Alder “click” chemistry in material synthesis is well-established, exploration of the strategy for constructing homopolymers using a single-component monomer system is almost completely unknown. Through the proposed studies, access to telechelic cyclopentadiene monomers that are otherwise impossible to prepare will become accessible. Furthermore, the development of the proposed reactions will broadly increase our fundamental understanding of this new approach that have important applications in many fields of chemistry. By developing a light-triggered approach to access cyclopentadiene, the new strategy will also provide the high-resolution spatial control over chemical functionalization required to pattern biomaterials and move beyond current state of the art. Altogether, the one- and two-component cyclopentadiene based materials will address a long-standing challenge of preparing homopolymers with a single component telechelic monomer, and serve as a valuable new addition to the arsenal of available Diels–Alder “click” reactions for preparing functional biomaterials with spatial and temporal control. To accomplish this work, the following specific aims will be pursued: (1) utilize on-demand, metal-free deprotection of norbornadiene with tetrazine to access and isolate cyclopentadiene based monomers for single-component Diels–Alder-based polymerization and (2) develop a photo-click platform based on photolabile norbornadiene–cyclopentadienone adducts for spatiotemporal introduction of cyclopentadiene in materials. 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.