DNA dynamics and flow properties are of great importance for understanding its functions. DNA is a semiflexible polymer chain characterized by having a large persistence length of around 50 nm and high charge density; DNA chains are interacting efficiently at high concentrations, in dependence of the ionic concentration. In relation with DNA molecular characteristics, it is also known that DNA solutions are able to form liquid crystalline phases over a critical polymer concentration. In this work, the supramolecular organization in calf-thymus DNA solution, with low degree of entanglement, appearing under flow was studied in a wide DNA concentration range from 2 to 10 mg/mL, at a pH of 7.3 and 20 °C. The rheological behavior of the system was studied using steady state flow and oscillatory measurements. Transient regimes were also tested by imposing controlled shear rates on a short time up to steady state. Furthermore, a combination of visual observations and flow birefringence measurements was proposed to reach a better understanding of the obtained rheological behavior. The presence of a shear-induced texture is revealed under flow for the calf-thymus DNA solutions at C DNA> 5 mg/mL and attributed to organized domains of DNA molecules, named in the text as crystalline parts, which are progressively oriented under shear. Finally, at high shear rates (over 100 s–1), it is shown that for the DNA solutions the orientation of these organized DNA domains and connecting chains under flow goes to an anisotropic monodomain.
Positively charged elastin-like polypeptides (ELPs) were synthesized for the compaction of genetic material. A recombinant ELP (VPGXG) 40 with X=V,M (3:1) was post-modified in two steps to introduce chemoselectively either primary or secondary amine pendant groups at each methionine residue. Positively charged ELPs were characterized by SDS-PAGE, size exclusion chromatography, 1 H NMR, potentiometric titrations and dynamic light scattering to assess their purity and determine their degree of functionalization, molecular weight, isoelectric point and thermo-responsive behaviour. Electrostatic complexation between the different ELP derivatives and nucleic acids was studied to determine the stoichiometry of ELP S /nucleic acids complex formation, and to find optimal conditions leading to stable nanoparticles with controlled size and surface potential. The stability of these complexes was investigated in the presence of salts at physiological concentrations and in the presence of surfactant. This study revealed that two regimes of stable nanoparticles in terms of size and charge can be obtained from the electrostatic complexation between the primary amine containing ELP derivative, ELP(-NH 2 ), and plasmid DNA. Resulting complexes were found to be stable to dissociation for charge ratios up to 2.5 under physiological salt concentrations (154 mM NaCl), showing that plasmid DNA was completely condensed by the polycationic ELP and protected against electrolyte-mediated dissociation.
This paper reports the use of polysaccharides extracted from seed of Persea americana var. Hass in the synthesis of acrylic hydrogels. The effects of the chemical composition (acrylamide/acrylic acid), the concentration of crosslinking agent (glycerol diacrylate) and the type of initiation (redox, photoinitiation) of the hydrogels were evaluated with and without polysaccharides. Xerogels were characterized by FTIR spectroscopy, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), while for the swollen hydrogels the swelling kinetic and mechanical properties were evaluated. The kinetic parameters were obtained using the second order equation proposed by Schott, where it is reported that by increasing the concentration of the crosslinking agent, the degree of swelling is reduced because of the greater structural level. The increase of the amount of acrylamide and the amount of polysaccharides causes also a decrease in the swelling degree. The type of initiation also affected the hydrogels swelling kinetic, the photoinitiated hydrogels were the ones that captured less water. Moreover, the increasing of the glass transition temperature and the compression modulus with the crosslinking agent concentration and molar ratio AAm/AAc are observed for hydrogels with and without polysaccharides. The results demonstrate a successful incorporation of polysaccharides into the polymeric network.
In this work, we have explored the use of hydrophobic deep eutectic systems (DESs) composed of d,l-menthol and different naturally occurring acids (acetic acid, lauric acid, lactic acid, and pyruvic acid) as an alternative green internal (dispersed) phase in the formulation of high internal phase emulsions (HIPEs). DES-in-water (DES/W) HIPEs were formulated using the hydrophilic monomer acrylamide and the cross-linker N,N′-methylenebis(acrylamide) with water as the continuous phase and stabilized with a nonionic triblock copolymer surfactant (Pluronic F127). Furthermore, HIPEs formulated with tetradecane as the dispersed phase were comparatively studied. Surprisingly, stable DES/W HIPEs were obtained with the d,l-menthol/acetic acid (M:AA) DES and used as templates to obtain polyacrylamide macroporous materials (polyHIPEs) within a sustainable framework. The materials were coated with maghemite nanoparticles (γ-Fe2O3 Nps; synthesized in situ onto the porous structure by a coprecipitation method), allowing the formation of hydrophilic polyHIPEs with magnetic and electrostatic properties, which were satisfactorily used as methylene blue (MB) dye adsorbents. The use of the M:AA DES as the internal phase in HIPE formulation allowed the synthesis of macroporous materials with higher surface area (S BET) and γ-Fe2O3 Nps amount than those formulated with tetradecane because of the different porous structures obtained. Therefore, the magnetic polyHIPEs obtained with the M:AA DES presented higher MB dye maximum adsorption capacity (359.71 mg g–1) than those with tetradecane (264.55 mg g–1) in the same synthesis conditions, even higher than some commercial MB adsorbents. The materials were reused for more than six adsorption/desorption cycles without losing their adsorption capacity. Thus, the M:AA DES represents a green tool for the preparation of magnetic macroporous materials composed of polyacrylamide γ-Fe2O3 Nps with a promising and competitive performance as MB dye adsorbents.
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.
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