Enzymatic synthesis of molecular complexes of polyaniline with DNA and synthetic oligonucleotides: Thermal and morphological characterization

The assembly of electronic and photonic materials on biomacromolecules is of tremendous interest for the development of biofunctional nanocomplexes as well as highly selective biosensors. In the context of the use of electrically conducting polymers for sensing, polyaniline (Pani) and polypyrrole have received considerable interest because of their well-known electrical properties. Recently, we have reported an enzyme catalyzed synthetic procedure involving horseradish peroxidase (HRP) for the polymerization of aniline on a calf thymus DNA matrix. The mild reaction conditions involved in the synthesis have provided opportunities for the use of more delicate biomacromolecules as templates. The complexation of Pani with DNA has been found to induce reversible changes in the secondary structure of DNA leading to the formation of an over-wound polymorph. The thermal characterization (melting behavior) of the DNA in the complex and the morphological properties of the complex have provided corroborative evidence for the wrapping of Pani around the DNA matrix. Scanning probe and electron microscopy studies have indicated that the formation of Pani causes the DNA-Pani strands to agglomerate, presumably due to the neutralization of charge on the phosphate groups by the partially charged Pani. We also report the synthesis of Pani on a synthetic oligonucleotide (Poly[dA-dC].poly[dG-dT]). Demonstration of the use of a new biomimetic catalyst, polyethylene glycol modified hematin (PEG-hematin), in these reactions will also be presented. These results indicate that this biocatalytic synthetic approach is generic, versatile and can be adopted for both genomic and synthetic nucleic acids.