Biomass RNA for the Controlled Synthesis of Degradable Networks by Radical Polymerization

Abstract

Nucleic acids extracted from biomass have emerged as sustainable and environmentally friendly building blocks for the fabrication of multifunctional materials. Until recently, the fabrication of biomass nucleic acid-based structures has been facilitated through simple crosslinking of biomass nucleic acids, which limits the possibility of material properties engineering. This study presents an approach to convert biomass RNA into an acrylic crosslinker through acyl imidazole chemistry. The number of acrylic moieties on RNA was engineered by varying the acylation conditions. The resulting RNA crosslinker can undergo radical copolymerization with various acrylic monomers, thereby offering a versatile route for creating materials with tunable properties (e.g., stiffness and hydrophobic characteristics). Further, reversible-deactivation radical polymerization methods, such as atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT), were also explored as additional approaches to engineer the hydrogel properties. The study also demonstrated the metallization of the biomass RNA-based material, thereby offering potential applications in enhancing electrical conductivity. Overall, this research expands the opportunities in biomass-based biomaterial fabrication, which allows tailored properties for diverse applications.

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

“…The versatility of this system was further demonstrated through successful polymerization with multiscale nucleic acid scaffolds, highlighting its potential for applications in materials science and biotechnology. By leveraging programmable self-assembly (e.g., toehold mediated strand displacement) and nucleic acid amplification techniques (e.g., polymerase chain reaction and rolling circle amplification), − we anticipate that the NuABD -based photocatalytic ATRP platform would open new opportunities such as stimuli-responsive polymerization, , nanofabrication, , and nucleic acid–polymer biohybrids. ,,, …”

Future Directions for Atom Transfer Radical Polymerizations

“…Acylation of OH-groups in RNA with either ATRP initiators or a polymerizable methacrylate/methacrylamide moiety presents new opportunity for bioconjugation . This has been applied not only to the synthetic RNA but also to the low-cost biomass-derived RNA, enabling the creation of selectively degradable hydrogels . Strong interactions between DNA and specific fluorescent dyes offer potential for new, selective photocatalytic systems.…”

Robust Miniemulsion PhotoATRP Driven by Red and Near-Infrared Light

“…A promising alternative would be adopting reversible deactivation radical polymerization (RDRP) techniques for emulsion polymerization. ,− Unlike FRP, propagating radicals in RDRP undergo reversible deactivation mediated by various RDRP-regulating agents (typically the Cu complex for atom transfer radical polymerization (ATRP), chain transfer agents for reversible addition–fragmentation chain transfer (RAFT) polymerization, and alkoxyamine for nitroxide-mediated polymerization (NMP)). This prolongs the lifetime of propagating radicals, compressing undesired chain terminations. − Consequently, this affords precise control over molecular weight, dispersity, sequence, end group functionality, and architecture. − These advantages have propelled the practical implementation of RDRP in dispersed media. , The aqueous dispersed polymerization can generally be categorized as microemulsion, miniemulsion, emulsion, suspension, dispersion, and precipitation polymerization. These different techniques of dispersed polymerization are distinguished based on the initial state of the polymerization mixture, the kinetics of the polymerization process, the mechanism of particle formation, and the size of the resulting particles. ,, …”