Dielectric relaxation of DNA aqueous solutions

We report on a detailed characterization of complex dielectric response of Na-DNA aqueous solutions by means of low-frequency dielectric spectroscopy (40 Hz - 110 MHz). Results reveal two broad relaxation modes of strength 20<\Delta\epsilon_LF<100 and 5<\Delta\epsilon_HF<20, centered at 0.5 kHz<\nu_LF<70 kHz and 0.1 MHz<\nu_HF<15 MHz. The characteristic length scale of the LF process, 50<L_LF<750nm, scales with DNA concentration as c_DNA^{-0.29\pm0.04} and is independent of the ionic strength in the low added salt regime. Conversely, the measured length scale of the LF process does not vary with DNA concentration but depends on the ionic strength of the added salt as I_s^{-1} in the high added salt regime. On the other hand, the characteristic length scale of the HF process, 3<L_HF<50 nm, varyes with DNA concentration as c_DNA^{-0.5} for intermediate and large DNA concentrations. At low DNA concentrations and in the low added salt limit the characteristic length scale of the HF process scales as c_DNA^{-0.33}. We put these results in perspective regarding the integrity of the double stranded form of DNA at low salt conditions as well as regarding the role of different types of counterions in different regimes of dielectric dispersion. We argue that the free DNA counterions are primarily active in the HF relaxation, while the condensed counterions play a role only in the LF relaxation. We also suggest theoretical interpretations for all these length scales in the whole regime of DNA and salt concentrations and discuss their ramifications and limitations.Comment: 15 pages, 9 figure

Short-fragment Na-DNA dilute aqueous solutions: Fundamental length scales and screening

Dielectric spectroscopy is used to investigate fundamental length scales of 146 bp short-fragment (nucleosomal) dilute Na-DNA solutions. Two relaxation modes are detected: the high- and the low-frequency mode. Dependence of the corresponding length scales on the DNA and on the (uni-valent) salt concentration is studied in detail, being different from the case of long, genomic DNA, investigated before. In low-added-salt regime, the length scale of the high-frequency mode scales as the average separation between DNAs, though it is smaller in absolute magnitude, whereas the length scale of the low-frequency mode is equal to the contour length of DNA. These fundamental length scales in low-added-salt regime do not depend on whether DNA is in a double-stranded or single-stranded form. On the other hand, with increasing added salt, the characteristic length scale of the low-frequency mode diminishes at low DNA concentrations probably due to dynamical formation of denaturation bubbles and/or fraying in the vicinity of DNA denaturation threshold

Manning free counterion fraction for a rodlike polyion: Aqueous solutions of short DNA fragments in presence of very low added salt

We quantified the Manning free (uncondensed) counterions fraction θ for dilute aqueous solutions of rodlike polyions: 150 bp DNA fragments, in the presence of a very low concentration of monovalent salt c salt &lt; 0.05 mM. Conductivity measurements of these solutions for DNA base pair concentration range 0.015 c 8 mM were complemented by fluorescence correlation spectroscopy (FCS) measurements of the DNA polyion diffusion coefficient D p (c). We observed a crossover in the normalized conductivity σ (c)/c that nearly halved across the c = 0.05-1 mM range, while D p (c) remained rather constant, as we established by FCS. Analyzing these data we extracted θ (c) = 0.30-0.45, and taking the Manning asymmetry field effect on polyelectrolyte conductivity into account we got θ (c) = 0.40-0.60. We relate the θ(c) variation to gradual DNA denaturation occurring, in the very low salt environment, with the decrease in DNA concentration itself. The extremes of the experimental θ (c) range occur toward the highest, above 1 mM, and the lowest, below 0.05 mM, DNA concentrations and correspond to the theoretical θ values for dsDNA and ssDNA, respectively. Therefore, we confirmed Manning condensation and conductivity models to be valuable in description of dilute solutions of rodlike polyions