The multifunctional monomers 5‘-methacryloyluridine and 5‘-methacryloyladenosine have
been polymerized under atom transfer polymerization conditions, giving products of narrow polydispersities
as consistent with living polymerization. Initiators derived from both uridine and adenosine have also
been used to terminally functionalize poly(methyl methacrylate) and poly(styrene). Both hydroxyl-protected
and unprotected initiators successfully gave polymers of predictable and narrow PDI. Atom transfer
polymerization of methyl methacrylate with the protected 5‘-bromoisobutyroyluridine initiator 2 with
NMPI ligand in conjunction with copper(I) bromide gives polymer with an M
n of 13 100 with a very narrow
PDI of 1.06 (M
n of 11 000 1H NMR). The initiator efficiency is less than unity (e.g., 0.81 for the above
reaction), similar to that observed with nonfunctional initiators. 1H NMR is used to demonstrate the
presence of the initiator in the polymer. The results demonstrate that this living polymerization system
is inert to a multitude of functionality in the initiator, including secondary hydroxyl, silyl ether, tertiary
amine, primary amine, secondary amide, etc. Atom transfer polymerization has been used to synthesize
well-defined poly(nucleoside)-based polymers which have tremendous potential for templating and
polymers used in applications that require biorecognition.
Poly(5‘-acryloyluridine) has been shown to act as a template in the radical polymerization
of the complementary 5‘-acryloyladenosine in the presence of the noncomplementary 5‘-acryloyluridine.
The template was synthesized by polymerizing 5‘-acryloyluridine using AIBN as the initiator. The 5‘-acryloylnucleosides were synthesized by regiospecific acylation of adenosine and uridine at the 5‘-position
using the enzyme Candida antarctica lipase 435 (CAL 435). The remaining hydroxyl groups were protected
as silyl ethers to increase the solubility in nonpolar solvents.
Copper(I) mediated radical polymerisation is used to polymerise uridine and adenosine substituted methacrylates onto a silica surface giving supported polymers with potential as re-usable templates and for interaction with nucleic acids.
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