Observations of three "re-entrant" twisted structures in double-stranded DNA dispersion particles.

In this work we report on observations of new twisted (cholesteric-like) structures in liquid-crystalline dispersion particles with a hexagonal packing of double-stranded (ds) DNA molecules. Heating up to 80 °C of the DNA dispersion formed in a aqueous-salt solution with a high osmotic pressure (concentration) of poly(ethylene glycol) induces the formation of a new, optically active, spirally twisted structure of these molecules ("re-entrant" cholesteric structure (rest-A structure)). Cooling of this dispersion up to 22 °C is accompanied by the formation of an additional "re-entrant" cholesteric structure (rest-B). Modification of particles of the ds DNA dispersion (with rest-B structure) by replacing Na+ cations by multi-charged Gd3+ cations results in the third " re-entrant" structure (rest-C) despite a high density packing of ds nucleic acid molecules.

Re-entrant cholesteric phase in DNA liquid-crystalline dispersion particles.

In this research, we observe and rationalize theoretically the transition from hexagonal to cholesteric packing of double-stranded (ds) DNA in dispersion particles. The samples were obtained by phase exclusion of linear ds DNA molecules from water-salt solutions of poly(ethylene glycol)-PEG-with concentrations ranging from 120 mg ml-1 to 300 mg ml-1. In the range of PEG concentrations from 120 mg ml-1 to 220 mg ml-1 at room temperature, we find ds DNA molecule packing, typical of classical cholesterics. The corresponding parameters for dispersion particles obtained at concentrations greater than 220 mg ml-1 indicate hexagonal packing of the ds DNA molecules. However, slightly counter-intuitively, the cholesteric-like packing reappears upon the heating of dispersions with hexagonal packing of ds DNA molecules. This transition occurs when the PEG concentration is larger than 220 mg ml-1. The obtained new cholesteric structure differs from the classical cholesterics observed in the PEG concentration range 120-220 mg ml-1 (hence, the term 're-entrant'). Our conclusions are based on the measurements of circular dichroism spectra, X-ray scattering curves and textures of liquid-crystalline phases. We propose a qualitative (similar to the Lindemann criterion for melting of conventional crystals) explanation of this phenomenon in terms of partial melting of so-called quasinematic layers formed by the DNA molecules. The quasinematic layers change their spatial orientation as a result of the competition between the osmotic pressure of the solvent (favoring dense, unidirectional alignment of ds DNA molecules) and twist Frank orientation energy of adjacent layers (favoring cholesteric-like molecular packing).

Nanoconstructions based on double-stranded nucleic acids.

We describe the formation and properties of nanoconstruction that consists of the double-stranded DNA molecules located at distance of 35-50 A in the spatial structure of particles of their cholesteric liquid-crystalline dispersions and cross-linked by artificial nanobridges. The resulting nanostructures possess the peculiar spatial and optical properties.