Constituent- and Composition-Dependent Surfactant Aggregation in (Lanthanide Salt + Urea) Deep Eutectic Solvents

Due to the ease of tailoring the physicochemical properties by simply changing a constituent or composition, deep eutectic solvents (DESs) possess widely varying capabilities for surfactant self-assembly that could depend on the surfactant headgroup charge. The self-aggregation process of three surfactants, sodium dodecylsulfate (SDS), cetyltrimethylammonium bromide (CTAB), and Triton X-100 (TX-100), dissolved in DESs composed of a lanthanide salt (Ln) and urea (U) is investigated. The role of the identity of the metal salt is assessed by using [La(NO3)3·6H2O] (La) and [Ce(NO3)3·6H2O] (Ce) and that of the composition is deciphered by systematically changing the mole ratio of the metal salt and urea in (La/U) DESs. The response to a fluorescence probe pyrene-1-carboxaldehyde along with electrical conductance and surface tension measurements is used to obtain the critical aggregation concentration (CAC). While the CACs in 1:3.5 (Ln/U) for SDS are significantly lower than that in water, the values are marginally higher for CTAB and TX-100. The CACs for all three surfactants are similar in 1:3.5 (La/U) and (Ce/U) DESs, implying that the identity of the metal in the salt is not so important. Increasing the urea composition in (La/U) DESs results in increased CAC for SDS and CTAB; however, a minimal decrease in CAC is observed for TX-100. From the temperature dependence of CAC, thermodynamic parameters, ΔGagg0, ΔHagg0, and ΔSagg0, of the surfactant self-aggregation process are estimated. These parameters reveal that while at a lower urea content, the SDS/CTAB self-assembly process is enthalpically driven, it becomes entropically favored at higher urea concentrations. The TX-100 self-aggregation in these DESs is found to be strongly enthalpically favored and entropically un-favored. These parameters are explained as a combination of passage of the solvophobic surfactant chain from the bulk DES to the aggregate pseudo-phase and differential orientation/organization of DES constituents around surfactant monomers and/or aggregates.