Nucleic Acid-Binding Dyes as Versatile Photocatalysts for Atom-Transfer Radical Polymerization

Abstract

Nucleic acid-binding dyes (NuABDs) are fluorogenic probes that light up after binding to nucleic acids. Taking advantage of their fluorogenicity, NuABDs have been widely utilized in the fields of nanotechnology and biotechnology for diagnostic and analytical applications. We demonstrate the potential of NuABDs together with an appropriate nucleic acid scaffold as an intriguing photocatalyst for precisely controlled atom-transfer radical polymerization (ATRP). Additionally, we systematically investigated the thermodynamic and electrochemical properties of the dyes, providing insights into the mechanism that drives the photopolymerization. The versatility of the NuABD-based platform was also demonstrated through successful polymerizations using several NuABDs in conjunction with diverse nucleic acid scaffolds, such as G-quadruplex DNA or DNA nanoflowers. This study not only extends the horizons of controlled photopolymerization but also broadens opportunities for nucleic acid-based materials and technologies, including nucleic acid−polymer biohybrids and stimuli-responsive ATRP platforms.

Highly efficient dual photoredox/copper catalyzed atom transfer radical polymerization achieved through mechanism-driven photocatalyst design

“…According to the previous literature 53 – 58 , PC regeneration is assumed to primarily occur through the oxidation of TPMA. However, given the redox potentials, not only TPMA but also Cu(I)Br/L with bromide and propagating radical species with bromide can regenerate the PC (see Supplementary Fig.…”

“…1a , Mechanism I). As the ligand undergoes oxidation, it facilitates the regeneration of PC 53 – 58 . Cu(I)Br/L and propagating radical species, along with bromide, can also promote PC regeneration through termolecular processes.…”