Ordered phases in concentrated DNA solutions

Aqueous solutions of concentrated DNA, a strong polyelectrolyte, in 1:1 electrolyte form liquid-crystalline phases analogous to those observed for other semi-rigid neutral polymers and weak polyelectrolytes. Phase transitions were examined in detail for DNA fragments with a contour length (500 Å) approximating the persistence length. These fragments form at least three lyotropic phases. The lowest density or “precholesteric” phase appears to be a nematic with a slight and easily variable twist. The intermediate density phase is a true cholesteric with a pitch of ≈2.1 μm. With increasing concentration the cholesteric phase unwinds prior to formation of the third, high density, columnar phase. Phase transition boundaries were determined as functions of DNA concentration from 10 to 300 mg/ml solvent, supporting electrolyte concentration from 0.01 to 1.0 M, and temperature from 20°C to 60°C. Critical concentrations for formation of anisotropic phase (Ci) and disappearance of isotropic phase (Ca) were only moderately dependent on temperature. Ci, Ca, and the pitch of the cholesteric phase were surprisingly insensitive to the supporting electrolyte concentration. The insensitivity can be most simply related to the high concentrations required for anisotropic phase formation by these rather short, highly charged rod-like DNA fragments. At high concentrations the DNA counterions contribute significantly to the effective ionic strength, hence overall charge screening, and the counterion atmosphere as monitored by 23Na NMR, appears to be perturbed by inter-rod interactions.