Precise Sequence Control in Linear and Cyclic Copolymers of 2,5-Bis(2-thienyl)pyrrole and Aniline by DNA-Programmed Assembly

Abstract

A series of linear and cyclic, sequence controlled, DNA-conjoined copolymers of aniline (ANi) and 2,5-bis(2-thienyl)pyrrole (SNS) were synthesized. In one approach, linear copolymers were prepared from complementary DNA oligomers containing covalently attached SNS and ANi monomers. Hybridization of the oligomers aligns the monomers in the major groove of the DNA. Treatment of the SNS- and ANi-containing duplexes with horseradish peroxidase (HRP) and H2O2 causes rapid and efficient polymerization. In this way, linear copolymers (SNS)4(ANi)6 and (ANi)2(SNS)2(ANi)2(SNS)2(ANi)2 were prepared and analyzed. A second approach to the preparation of linear and cyclic copolymers of ANi and SNS employed a DNA encoded module strategy. In this approach, single-stranded DNA oligomers composed of a central region containing (SNS)6 or (ANi)5 covalently attached monomer blocks and flanking 5'- and 3'-single-strand DNA recognition sequences were combined in buffer solution. Self-assembly of these oligomers by Watson-Crick base pairing of the recognition sequences creates linear or cyclic arrays of SNS and ANi monomer blocks. Treatment of these arrays with HRP/H2O2 causes rapid and efficient polymerization to form copolymers having patterns such as cyclic BBA and linear ABA, where B stands for an (SNS)6 block and A stands for an (ANi)5 block. These DNA-conjoined copolymers were characterized by melting temperature analysis, circular dichroism spectroscopy, native and denaturing polyacrylamide gel electrophoresis, and UV-visible-near-IR optical spectroscopy. The optical spectra of these copolymers are typical of those of conducting polymers and are uniquely dependent on the specific order of monomers in the copolymer.