The properties of negatively charged mucin in aqueous solutions and its interaction with anionic sodium alkyl sulfates with different hydrocarbon chain lengths were studied by means of dynamic light scattering. It was observed that mucin forms aggregates in aqueous solutions with a hydrodynamic radius above 500 nm. These aggregates dissolve when sodium dodecyl sulfate or sodium decyl sulfate is present at sufficiently high concentration, above about 0.2 cmc (critical micellar concentration). On the other hand, sodium octyl sulfate is not very effective in dissolving the mucin aggregates. The hydrodynamic radius of the dissolved mucin, decorated with some associated surfactant, is found to be in the range of 40−90 nm. The observation that the dissolving power of the sodium alkyl sulfates decreases with decreasing surfactant chain length suggests that the association between the surfactant and mucin is hydrophobically driven. The kinetics of the dissolution process depends on the surfactant concentration, a higher surfactant concentration giving rise to a more rapid dissolution of the aggregates. It was also observed that when the ionic strength is increased, the surfactant concentration needed to dissolve the mucin aggregates decreases. This can be explained by reduction of repulsive electrostatic forces by the salt.
Solvent isotope effects on the interaction between the hyperbranched cationic polyelectrolyte, polyethylene imine (PEI), and the anionic surfactant sodium dodecyl sulfate (SDS) were investigated using potentiometric titration and eletrophoretic mobility measurements. In the basic pH range, a significantly higher fraction of the amine groups was found to be protonated when the PEI was dissolved in D2O compared to H2O at the same pH/pD. The difference in polymer charge in the two solvents decreases gradually with decreasing pH, and it completely diminishes at around pH = 4. Electrophoretic mobility measurements of PEI/SDS complexes at different pH values correlated very well with these observations. At pH/pD approximately 9 a much higher mobility of the PEI/SDS complexes was found in D2O than in H2O at low surfactant concentrations, and the charge neutralization point shifted to a considerably larger surfactant concentration in heavy water. These results can be explained by the significantly higher charge density of the PEI in D2O compared to H2O. However, at the natural pH/pD as well as at pH = 4 and pD = 4 conditions the PEI molecules have roughly equal charge densities, which result in very similar charged characteristics (mobilities) of the PEI/SDS complexes as well as the same charge neutralization SDS concentration. It can be concluded that extreme care must be taken in the general analysis of those experiments in which weak polyelectrolyte/surfactant aggregates are investigated in heavy water, and then these observations are correlated with structures of the same system in water.
The association between mucin and surfactants at the solid-liquid interface has been investigated employing reflectometry. The study is particularly aimed at understanding the removal of preadsorbed mucin layers by surfactant addition. To this end we investigated the effect of three different surfactants, one anionic surfactant, sodium dodecylsulfate (SDS), and two nonionic ones, penta(oxy ethylene) dodecyl ether (C12E5) and n-dodecyl β-D-maltopyranoside (C12-mal). All three surfactants were found to be potent in removing mucin from hydrophobic surfaces. On the other hand, C12-mal was found to have a very limited effect on mucin adsorbed to hydrophilic negatively charged surfaces, whereas the mucin layer was removed by SDS and C 12E5. The association between mucin and the three different surfactants was also investigated by means of dynamic light scattering and surface tension measurements. It was concluded that SDS associates readily with mucin above a critical surfactant concentration, about 0.2 cmc, whereas the nonionic surfactants associate with mucin to a very limited degree. The results obtained with the different techniques allow us to propose that C 12E5 removes mucin from silica surfaces by competitive adsorption, whereas the removal of mucin by SDS is due to formation of mucin/SDS complexes that have reduced surface affinity and increased water solubility compared to mucin alone.
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