Effect of Complementary Nucleobase Interactions on the Copolymer Composition of RAFT Copolymerizations.

Methacryloyl-type monomers containing adenine and thymine have been successfully synthesized with good yields. The homopolymerization and copolymerization of these two new functional monomers were carried out using RAFT polymerization. The reactivity ratios of monomer pairs were measured and calculated using a nonlinear least-squares (NLLS) method, and the results confirmed that the monomer reactivities were dependent on the solvent used for polymerization. The presence and absence of hydrogen bonding affected the resultant copolymer composition where moderate alternating copolymers had a tendency to be formed in CHCl, while in DMF, statistical copolymers were formed. Furthermore, the glass transition temperatures of the copolymers were investigated, and the self-assembly of block copolymers made in solvents with different polarity were studied.