Hydration Shells of DNA from the Point of View of Terahertz Time-Domain Spectroscopy.

Hydration plays a fundamental role in DNA structure and functioning. However, the hydration shell has been studied only up to the scale of 10-20 water molecules per nucleotide. In the current work, hydration shells of DNA were studied in a solution by terahertz time-domain spectroscopy. The THz spectra of three DNA solutions (in water, 40 mm MgCl2 and 150 mM KCl) were transformed using an effective medium model to obtain dielectric permittivities of the water phase of solutions. Then, the parameters of two relaxation bands related to bound and free water molecules, as well as to intermolecular oscillations, were calculated. The hydration shells of DNA differ from undisturbed water by the presence of strongly bound water molecules, a higher number of free molecules and an increased number of hydrogen bonds. The presence of 40 mM MgCl2 in the solution almost does not alter the hydration shell parameters. At the same time, 150 mM KCl significantly attenuates all the found effects of hydration. Different effects of salts on hydration cannot be explained by the difference in ionic strength of solutions, they should be attributed to the specific action of Mg2+ and K+ ions. The obtained results significantly expand the existing knowledge about DNA hydration and demonstrate a high potential for using the THz time-domain spectroscopy method.

Effective Medium Model Applied to Biopolymer Solutions.

Studying dielectric properties of heterogeneous systems is challenged by a problem of uncertainty of the ratio between dielectric permittivity of the system and dielectric permittivities of its components. Such ratios can be obtained in some cases using theoretical effective medium models. However, such models have not yet been developed for all the systems possible. Particularly, there is no effective medium model with filamentary inclusions. Such a theoretical model elaborated based on the fundamental principles of electrodynamics of continuous media is suggested in the present work. Any point of a filamentary inclusion with a length that is significantly greater than the thickness can be regarded as being located in a long cylinder-like fragment of the inclusion with stochastic direction of the cylinder axis relative to the external electric field. With this regard, electric field strength and electric induction values were averaged across the entire volume of a two-phase dielectric material. As a result, a model linking the dielectric permittivity of the two-phase system and the dielectric permittivities of both phases was elaborated. The model appears to be highly relevant for studying solutions of biopolymers, such as nucleic acids, fibrillar proteins and protein aggregates, polysaccharides, by means of electrical impedance spectroscopy, dielectric spectroscopy, and terahertz time-domain spectroscopy. The suggested theoretical model was successfully validated on a DNA solution within the terahertz region.