Propagation of Chirality in Mixtures of Natural and Enantiomeric DNA Oligomers

Abstract

Concentrated solutions of ultrashort duplex-forming DNA oligomers may develop various forms of liquid crystal ordering among which is the chiral nematic phase, characterized by a macroscopic helical precession of molecular orientation. The specifics of how chirality propagates from the molecular to the mesoscale is still unclear, both in general and in the case of DNA-based liquid crystals. We have here investigated the onset of nematic ordering and its chiral character in mixtures of natural D-DNA oligomers forming right-handed duplex helices and of mirror symmetric (L-DNA) molecules, forming left-handed helices. Since the nematic ordering of DNA duplexes is mediated by their end-to-end aggregation into linear columns, by controlling the terminals of both enantiomers we could study the propagation of chirality in solutions where the D and L species form mixtures of homochiral columns, and in solutions of heterochiral columns. The two systems behave in markedly different fashion. By adopting a simple model based on nearest-neighbor interactions, we account for the different observed dependence of the chirality of these two systems on the enantiomeric ratio.