Self-Assembled Bolaamphiphile Fibers Have Intermediate Properties between Crystalline Nanofibers and Wormlike Micelles: Formation of Viscoelastic Hydrogels Switchable by Changes in pH and Salinity

Abstract

The aggregation behavior and rheological properties of aqueous suspensions of the bolaamphiphile dotriacontane-1,32-diyl-bis[2-(dimethylammonio)ethylphosphate] (Me(2)PE-C32-Me(2)PE) were investigated depending on the pH value and the salinity by means of differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and oscillatory rheology. This bolaamphiphile self-assembles into helical fibers of approximately 5 nm thickness with an all-trans conformation of the alkyl chains. These nanofibers can gel water very effectively by forming a three-dimensional network. The headgroups' protonation depends on the pH value of the solution and influences the ability of the molecules to aggregate into fibers. At low pH values the headgroups are zwitterionic and stable hydrogels are formed, whereas at high pH values the headgroups are negatively charged and the length of the fiber aggregates diminishes as does the stability of the gel structure. We can show that by the addition of cations it is possible to shield the repulsive interaction between the molecules at high pH values so that the formation of the fiber aggregates and the gelation of the system occur. By addition of salt at high pH values the viscous flow behavior of Me(2)PE-C32-Me(2)PE suspensions could be transformed into the viscoelastic behavior of a gel. The gels show characteristics that are common in systems of wormlike micelles. However, there are also significant differences that arise from the unique bolaamphiphile fiber structure with highly ordered alkyl chains that render the properties similar to crystalline nanofibers.