Double helical conformation and extreme rigidity in a rodlike polyelectrolyte

The ubiquitous biomacromolecule DNA has an axial rigidity persistence length of similar to 50 nm, driven by its elegant double helical structure. While double and multiple helix structures appear widely in nature, only rarely are these found in synthetic non-chiral macromolecules. Here we report a double helical conformation in the densely charged aromatic polyamide poly (2,2'-disulfonyl-4,4'-benzidine terephthalamide) or PBDT. This double helix macromolecule represents one of the most rigid simple molecular structures known, exhibiting an extremely high axial persistence length (similar to 1 micrometer). We present X-ray diffraction, NMR spectroscopy, and molecular dynamics (MD) simulations that reveal and confirm the double helical conformation. The discovery of this extreme rigidity in combination with high charge density gives insight into the self-assembly of molecular ionic composites with high mechanical modulus (similar to 1 GPa) yet with liquid-like ion motions inside, and provides fodder for formation of other 1D-reinforced composites.