Physico-chemical study of new functionalized surfactants having thermo sensitive de-mixing behaviour: use in extraction of uranyl nitrate

New thermo-sensitive functionalized surfactants with metal-chelating properties have been developed and their physical-chemistry studied. They associate a polyethoxylated nonionic surfactant (CiEj) block and a amino-acid residue as a chelating group. Functionalization preserves both properties of the thermo-sensitive surfactant moiety and the chelating group, a diamide closed to uranyl ionophore.The complexing group participates to the polar head group of the surfactant, increasing the area per molecule. As a result, functionalized surfactants form spherical micelles when diluted in water, and the concentrated part of their phase diagrams exhibits structures having higher curvatures than the nonionic precursor CiEj. The structure of the uranyl - diamide complex has been elucidated by NMR and ESI-MS and is of the type UO2(NO3)2.L; the associated complexation constant, which is very low, has been evaluated by 1H NMR.A nitrate salt, LiNO3, is added at high concentration to improve complexation. The effect of this salt has been analyzed, and was found to be rather similar to the effect on classical CiEj. When uranyl nitrate complexation occurs, the cloud point decreases dramatically, together with the reduction of the area per head group at micelle/solution interface. This effect can be minimized by using a nonionic precursor having a larger polar head group. The functionalized surfactants have been tested in the cloud point extraction of uranyl nitrate, and have proved their efficiency. Those results demonstrate the viability of the functionalized surfactants design, with a covalent link between a thermo-sensitive surfactant block and a chelating group. (author)