Combining synthetic polymers with RNA paves the way for
creating
RNA-based materials with non-canonical functions. We have developed
an acylation reagent that allows for direct incorporation of the atom
transfer radical polymerization (ATRP) initiator into both short synthetic
oligoribonucleotides and natural biomass RNA extracted from torula
yeast. The acylation was performed in a quantitative yield. The resulting
initiator-functionalized RNAs were used for grafting polymer chains
from the RNA by photoinduced ATRP, resulting in RNA-polymer hybrids
with narrow molecular weight distributions. The RNA initiator was
used for the polymerization of oligo(ethylene oxide) methyl ether
methacrylate, poly(ethylene glycol) dimethacrylate, andN-isopropylacrylamide monomers, resulting in RNA bottlebrushes, hydrogels,
and stimuli-responsive materials. This approach, readily applicable
to both post-synthetic and nature-derived RNA, can be used to engineer
the properties of a variety of RNA-based macromolecular hybrids and
assemblies providing access to a wide variety of RNA-polymer hybrids.