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

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Abstract

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).

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Acknowledgements

The support from the Russian Science Foundation (project no. 16-15-00041) is gratefully acknowledged.

E.I. Kats's participation in the theoretical interpretation of the results was supported by the Russian Science Foundation (project no. 14-12-00475).

Our special thanks to Georgy S. Peters and Andrey Yu. Gruzinov for excellent support in the SAXS experiments at the DICSI station of the Kurchatov Synchrotron Radiation Source and Vladimir V. Volkov for support in the SAXS experiments on an AMUR-K laboratory diffractometer (Shubnikov Institute of Crystallography of the Russian Academy of Sciences).

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Authors and Affiliations

  1. Engelhardt Institute of Molecular Biology of the Russian Academy of Sciences, Vavilova St. 32, 119991, Moscow, Russia

    Yuri M. Yevdokimov, Sergey G. Skuridin & Viktor I. Salyanov

  2. National Research Centre ‘Kurchatov Institute’, Kurchatova Sq. 1, 123182, Moscow, Russia

    Sergey V. Semenov

  3. Shubnikov Institute of Crystallography of Federal Scientific Research Centre ‘Crystallography and Photonics’ of the Russian Academy of Sciences, Leninskii Ave. 59, 119333, Moscow, Russia

    Ljubov A. Dadinova

  4. Landau Institute for Theoretical Physics of the Russian Academy of Sciences, Kosygina St. 2, 119334, Moscow, Russia

    Efim I. Kats

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  1. Yuri M. Yevdokimov
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Yevdokimov, Y.M., Skuridin, S.G., Semenov, S.V. et al. Re-entrant cholesteric phase in DNA liquid-crystalline dispersion particles. J Biol Phys 43, 45–68 (2017). https://doi.org/10.1007/s10867-016-9433-4

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