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Polymers 2018, 10(11), 1204;

Role of Electrostatic Interactions on Supramolecular Organization in Calf-Thymus DNA Solutions under Flow

University Grenoble Alpes, CNRS, Grenoble INP, LRP, F-38000 Grenoble, France
Departamento de Ingeniería Química, Universidad de Guadalajara, Blvd. M. García Barragán #1451, Guadalajara C.P. 44430, México
CUTonalá, Departamento de Ingenierías, Universidad de Guadalajara, Nuevo Periférico #555 Ejido San José Tatepozco, Tonalá C.P. 45425, México
European Synchrotron Radiation Facility, 38000 Grenoble, France
Biomaterials Applications, 6 Rue Lesdiguières, 38000 Grenoble, France
Authors to whom correspondence should be addressed.
Received: 30 September 2018 / Revised: 23 October 2018 / Accepted: 24 October 2018 / Published: 28 October 2018
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Previous investigations were conducted on two concentrations of DNA solution: 4 mg/mL, for which it has been shown that no supramolecular organization is induced under flow at low shear rates; and 10 mg/mL, in which a liquid crystalline-type texture is formed under flow at low shear rates, attesting to an orientation of pre-organized chains. Rheological experiments are discussed and their results supported by small-angle X-ray scattering (SAXS) and flow birefringence visualization experiments. Scattering from polyelectrolytes has a characteristic signal, which is here observed in SAXS, showing a strong correlation peak between charged chains in water, for both concentrations. This peak is weaker in the presence of 0.01 M NaCl and suppressed in salt excess at 0.1 M NaCl. No plateau in the σ( γ ˙ ) plot was observed in analysis of rheological experiments on low DNA concentration (4 mg/mL). As typically observed in polyelectrolyte systems both the dynamic moduli and shear viscosity were higher in water as electrostatic forces dominate, than in the presence of salt, especially at low shear rates. The rheological results for concentrations of 0.01 M NaCl are lower than in water as expected due to partial screening of electrostatic repulsions. Rheological data for concentrations of 0.1 M NaCl are unexpected. Electrostatic forces are partially screened in the low salt concentration, leading to a drop in the rheological values. For high salt concentration there are no longer interchain repulsions and so steric interactions dominate within the entangled network leading to the subsequent increase in rheological parameters. Regardless of the solvent, at high shear rates the solutions are birefringent. In the 10 mg/mL case, under flow, textures are formed at relatively low shear rate before all the chains align going to a pseudonematic liquid crystalline phase at high shear rate. The electrostatic repulsion between semi-rigid chains induces a correlation between the chains leading to an electrostatic pseudo-gel in water and loosely in 0.01 M NaCl at low stress applied. To the best of our knowledge, this is the first time that such behavior is observed. In 0.1 M NaCl, DNA behavior resembles the corresponding neutral polymer as expected for polyelectrolyte in salt excess, exhibiting a yield stress. When texture appears in water and in 0.01 M NaCl, a critical transition is observed in rheological curves, where the viscosity decreases sharply at a given critical shear stress corresponding to a plateau in the σ( γ ˙ ) plot also observed in creep transient experiment. View Full-Text
Keywords: DNA; external ionic concentration; rheology; birefringence; SAXS; electrostatic interactions DNA; external ionic concentration; rheology; birefringence; SAXS; electrostatic interactions

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Bravo-Anaya, L.M.; Roux, D.C.D.; Soltero Martínez, J.F.A.; Carvajal Ramos, F.; Pignon, F.; Mannix, O.; Rinaudo, M. Role of Electrostatic Interactions on Supramolecular Organization in Calf-Thymus DNA Solutions under Flow. Polymers 2018, 10, 1204.

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