Deuterium isotope effects on the interaction between hyperbranched polyethylene imine and an anionic surfactant

• 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 gradually decreases 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≈9 a much higher mobility of the PEI/SDS complexes was found at low surfactant concentrations in D2O than in H2O, 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. On the other hand, at the natural pH/pD as well as at pH=4 and pD=4 conditions the PEI molecules have roughly equal charge density which results 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 where weak polyelectrolyte/surfactant aggregates are investigated in heavy water and then these observations are correlated with structures of the same system in water.

Nyckelord

Isotopic effects

polyethylene imine

PEI

sodium dodecyl sulfate

SDS

water

heavy water

electrophoretic mobility

charge density

polyelectrolyte

surfactant

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