Aggregation Behavior of Sodium Dioctyl Sulfosuccinate in Deep Eutectic Solvents and Their Mixtures with Water: An Account of Solvent's Polarity, Cohesiveness, and Solvent Structure.

An anionic surfactant sodium dioctyl sulfosuccinate (AOT) aggregates in deep eutectic solvents (DESs) and their mixtures with water (up to 50% w/w) in a contrasting manner. Two DESs, a mixture of choline chloride + urea and choline chloride + ethylene glycol, commonly known as Reline and Ethaline, respectively, are used as solvents. Behavior of AOT at air-solution interface and aggregation in bulk is investigated using surface tension, conductivity, fluorescence, and dynamic light scattering measurements. The obtained results are correlated with structural aspects of solvent systems as well as with inherent properties of solvent such as Kamlet-Taft polarity parameters, degree of cohesiveness derived from Gordon parameter (G), and cohesive energy density. It is observed that the spontaneity of aggregation in neat DESs or DES-water mixtures follows a trend reflected by various solvent parameters. However, characteristic properties of aggregation in water does not fit into this trend, where critical aggregation concentration of AOT is found in between 30 and 50% (w/w) of respective DES-water mixtures. (1)H NMR and (1)H-(1)H 2D NOESY spectroscopy is employed to get insights into reason behind this anomalous behavior. It is observed that AOT forms self-assembled structures similar to that of other surfactants in neat DESs, whereas it undergoes nanosegregation in DESs-water mixtures. The present results are expected to be useful for colloidal aspects of DESs and their mixtures with water.