Aggregation Behavior of Ethoxylated Phytosterol Surfactants in Different Protic Solvents: An Insight from Dielectric Relaxation Studies

The micellar aggregation behavior of biocompatible surfactants, phytosterol ethoxylates (BPS-n, n is the oxyethylene (EO) chain length), containing polyoxyethylene chains in four organic solvents (glycerol (G), ethylene glycol (EG), formamide (FA), and N,N-dimethylformamide (DMF)) was studied by dielectric spectroscopy in the frequency range of 40 Hz to 110 MHz. Only the BPS-n/EG and BPS-n/G systems show distinct dielectric loss peaks near 10(4) Hz, indicating that BPS-n forms micellar aggregates in EG and G solvents, and the interfacial polarization (IP) between the aggregates and solvents leads to this relaxation. The dielectric spectra were analyzed based on the IP theory and a columnar dispersion model. The dielectric parameters of micelles, the permittivity and conductivity of micelles and solvents, and the volume fraction of the aggregates in solvents were calculated. On this basis, the binding numbers of each EO group on the hydrophobic chain to the solvent molecules EG and G were calculated to be 0.42 and 0.22, respectively. It was suggested that the aggregation appears to be related to the magnitude of the hydrogen bonding interactions. The lower number of EO group-binding solvents is because of the strong steric effect of alcohol solvents and the magnitude of the hydrogen bonding force.