Core-shell inversion by pH modulation in dynamic covalent micelles.

Dynamic covalent surfactants have been obtained by the reversible condensation of a hydrophobic aldehyde (ended by an ionic tip) with various neutral polyethylene glycol based hydrophilic amines. In water, the duality between the two hydrophilic domains (charged and neutral) leads to their segregation when the surfactants are self-assembled within micelles. Depending on the number of polyethylene glycol units, a core-shell inversion leading to a switching orientation of the ionic tips from the inside to the outside of the micelles has been demonstrated by a combination of scattering techniques. In competition experiments, when several amines of different pKas and hydrophilic polyethylene glycol chains are competing for the same aldehyde, it becomes possible to trigger this core-shell inversion by pH modulation and associated dynamic constitutional reorganization.

Sedimentation stability and aging of aqueous dispersions of Laponite in the presence of cetyltrimethylammonium bromide.

This work discusses the sedimentation stability and aging of aqueous suspensions of Laponite in the presence of cetyltrimethylammonium bromide (CTAB). The concentration of Laponite was fixed at a constant level C(l)=2%wt, which corresponds to the threshold between equilibrium gel IG(1) and glass IG(2) states. The concentration of CTAB C(s) was within 0-0.3 %wt. In the presence of CTAB, the Laponite aqueous suspensions were unstable against sedimentation and separated into the upper and bottom layers (U and B layers, respectively). The dynamic light-scattering technique has revealed that addition of CTAB even at a rather small concentration, C(s)=0.0164 %wt (0.03 cation exchange capacity), induced noticeable changes in the aging dynamics of the U layer. It was explained by equilibration of CTAB molecules that were initially nonuniformly distributed between different Laponite particles. Accelerated stability analysis by means of analytical centrifugation with rotor speed ω=500-4000 rpm revealed three sedimentation regimes: continuous (I, C(s)<0.14 %wt), zonelike (II, 0.140.2%wt). It was demonstrated that the B layer was "soft" in the zonelike regime. The increase of ω resulted in its supplementary compressing and collapse of "soft" sediment above certain critical centrifugal acceleration. The physical nature of the observed behavior, accounting for enhancement of hydrophobic interactions between Laponite particles, is discussed.

Structural and dynamical properties of ribbonlike self-assemblies of a fluorinated cationic surfactant.

The structural and dynamic properties of low ionic strength micellar solutions of the cationic surfactant perfluorooctylbutane trimethylammonium bromide have been investigated by cryo-TEM, small-angle neutron scattering, small-angle X-ray scattering, T-jump and rheological experiments. The surfactant molecules self-assemble into narrow ribbons with average dimensions on the order of 4 nm x 3 nm, either under salt-free conditions or in the presence of up to 30 mM KBr or NaF. Cryo-TEM also reveals in the salt-free systems the presence of networks of multiconnected micelles. Rheological experiments showed that these surfactant systems exhibit a strong shear-thickening effect even in the presence of up to 30 mM KBr. The T-jump response of the micellar solutions was found to be multiexponential. This observation rules out the presence of only linear micelles with an exponential length distribution and suggests more complex topologies of the micellar aggregates. The relaxation time associated with the predominant process in the T-jump relaxation is strongly correlated to the critical shear rate beyond which shear thickening occurs, thus indicating that this critical shear rate is controlled by the micellar kinetics.