In the field of inherently conducting polymers,polyaniline (Pani) has elici
ted tremendous interest due to its promising electrical properties and uniq
ue redox tunability. Synthetic routes involving the use of polyelectrolytes
have significantly improved the processability of polyaniline. Recently,a
template guided synthesis catalyzed by an enzyme, horseradish peroxidase (H
RP), has provided a means of polymerizing aniline under milder pH condition
s (pH 4.3) and subsequently widened the. choice of templates to more delica
te biological macromolecules. Here we report a strategy that exploits the i
nherent molecular order as well as the polyelectrolyte behavior of DNA to e
nzymatically synthesize and biologically assemble conducting polyaniline. T
his "wrapping" of polyaniline on DNA has been. found to induce reversible c
hanges in the secondary structure of DNA, leading to the formation of an ov
er-wound polymorph. The polyaniline synthesized on the DNA also exhibited a
template-induced macroasymmetry. This unique polyaniline/DNA intertwined c
omplex has been used to "probe" and control the conformation of the DNA dou
ble helix.