Functionalization of DNA by Electrostatic Interactions: From Secondary Structures to Catalysis

The research presented in this doctoral thesis introduces a novel noncovalent PEGylation strategy that facilitates metal-free Watson-Crick and Hoogsteen hydrogen bonding-driven secondary structure formation in water and polar protic organic solvents. Our approach demonstrates that high-density PEGylation not only preserves functionality but also stabilizes secondary structures, potentially leading to new noncovalent nucleic acid-PEG hybrid architectures for biomedical applications. However, further research on the morphology, brush thickness, and persistence length of these new architectures, along with a thorough investigation of cation-induced dePEGylation, is essential for their biological applications. Moreover, we believe this approach expands the scope for functional DNA systems, including DNA nanostructures, in salt-free or low-ionic strength aqueous media. Ultimately, the reported electrostatic PEGylation method enables the fabrication of active DNA-based supramolecular catalysts and serves as a blueprint for extending the application of functional supramolecular DNA architectures to organic solvents and solvent-free environments.