DNA Nanoscaffold Catalysts for Selective Synthesis of Energetic Materials
Abstract
The purpose of this action is to add FY23 CR#1 (YIP) funds, in the amount of $50,000.00, for a new Grant with the University of Wisconsin. GRANT#13638484. The Program Officer is Chad Stoltz, (703) 696-0437, chad.a.stoltz.civ@us.navy.mil.--There is an ongoing need in energetic materials for mild synthetic reactions to generate nitrogen-rich molecules, including stereo-and regio-selective cyclizations and site-specific functionalization of complex substrates. Each of these goals is extremely challenging for conventional synthetic catalysts. In contrast, naturally occurring enzymes routinely catalyze analogous transformations under mild conditions with high specificity. However, enzymes tend to be specific for their evolved substrates, and they are limited tothe natural amino acids and cofactors, which restricts the scope of reactions they can catalyze. Supramolecular synthetic catalyststhat mimic enzymes could potentially combine the selectivity of enzymes with the expanded reactivity of synthetic catalysts. Creating such enzyme-mimicking catalysts requires architectures in which multiple reactive groups are displayed into a three-dimensional active site. DNA is a promising building material for the creation of such supramolecular enzyme mimicking catalysts because of the following advantages:--Predictable self-assembly of 3D nanostructures featuring cavities with diverse sizes and shapes--Diverse abiotic groups can be attached site-specifically on supramolecular DNA architectures--DNA is chiral and can be exploited for selective reactionsHere, I propose a research program using DNA nanostructures attached to abiotic groups for catalytic methodology. In Aim 1, Ipropose the rapid discovery of DNA-based catalysts that operate under mild conditions. In Aims 2 and 3, I propose to optimize the DNA scaffolds to enable selective transformations of interest for energetic materials.If successful, this research program will have a transformative impact on synthetic methodology, enabling discovery of new catalytic methods compatible with mild reaction conditions while harnessing the structural diversity and tunability of DNA nanostructures.This proposal has the long-term potential to transform the discovery of synthetic catalysts for important reactions in energetic materials, including C#N bond-forming reactions. Our proposed combinatorial method would dramatically reduce accelerate the discovery process while reducing environmental impact. Because the DNA nano-scaffolds resemble enzymes, they should operate efficiently under mild reaction conditions, thus minimizing energy consumption. Importantly, although the DNA nano-scaffold platform is unprecedented, it will be feasible to develop because it combinesestablished technologies from multiple disciplines. The DNA nano-scaffold platform may ultimately enable discovery of catalysts with diverse applications beyond synthetic methodology on complex substrates, including fuel synthesis, generation of novel plastics, and remediation of toxic agents. In addition, because DNA is a programmable material that can change conformation in response to specific stimuli, catalysts discovered using our approach could be used in the future within responsive materials. The impact of this work will extend beyond the specific applications of the nanoscaffold catalysts; the biggest impact may arise from elucidating fundamental principles in enzyme-mimicking catalysis and influencing other researchers pursuing this long-sought goal.*Approved for publicrelease
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Jan 12, 2023
- Source ID
- N000142312039
Entities
People
- Jeffrey Martell
Organizations
- Office of Naval Research
- United States Navy
- University of Wisconsin System