Leveraging pyrimidinone-Dewar Pyrimidinone Isomerization to Develop Novel Bioderived Polymers

With the support of the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Dr. Noah Burns and Dr. Yan Xia of Stanford University will investigate a new class of environmentally friendly polymers derived from molecules that form naturally in DNA when exposed to sunlight. This research will explore how light and heat can transform these molecules, known as pyrimidinones, between two different forms. This process should result in profound changes to the physical properties of materials made from these compounds, including strength, flexibility, and conductivity. These transformations are reversible and occur without producing waste, which could lead to smart plastics that respond to their surroundings and are easier to recycle. In addition to addressing the urgent need for sustainable materials with novel properties, this work will generate foundational knowledge that may guide the design of next-generation sustainable materials built from naturally abundant, bioderived molecular structures. Importantly, it will also foster broader scientific impact by supporting science education and outreach through multidisciplinary graduate student training as well as mentorship of undergraduates and high school students. The proposed research aims to develop innovative polymers by leveraging the unique chemical properties of 2-pyrimidinones and their photochemically derived Dewar isomers. 2-Pyrimidinones are a common class of bioderived aromatic heterocycles, yet they remain virtually unexplored in polymer design. Upon exposure to light, these conjugated, polar molecules can isomerize into nonconjugated, nonpolar, puckered Dewar structures—a transformation that is reversible with heat or acid. This project will systematically investigate the photochemical and thermal interconversion between a family of 2-pyrimidinones and their Dewar counterparts and harness this dynamic process to create polymers with tunable thermomechanical, rheological, and optoelectronic properties. Through a combination of modular synthesis, computational analysis, and polymer characterization, this research will establish foundational design principles for using these underexplored heterocycles in macromolecular chemistry. The results are expected to impact not only stimuli-responsive materials but also the broader development of sustainable polymers derived from non-petrochemical sources. 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.