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Cationic surfactants form complexes with DNA in aqueous solutions. In the case of single-chain surfactants that self-assemble into micelles, these complexes have a two-dimensional columnar structure. We have studied the structural polymorphism of such complexes by varying the chain length of the surfactant. A variety of columnar structures are observed, such as square, hexagonal and superhexagonal. Formation of these different structures can be qualitatively understood in terms of the interplay between entropic and electrostatic contributions to their free energy.

Columnar liquid crystalline phases of surfactant-DNA complexes