Solute-solvent contact by intermolecular cross-relaxation. 2. The water-micelle interface and the micellar interior.
The intermolecular dipole-dipole cross-relaxation is measured between 19F nuclei of sodium perfluorooctanoate in micelles and 1H nuclei of the water solvent. The cross-relaxation rates for fluorines in the different moieties along the surfactant vary strongly by the resonance frequency in the investigated range of 188-470 MHz. This frequency dependence indicates that the cross-relaxation between water and amphiphilic aggregates is not controlled solely by the fast local water dynamics but significantly contributed to by the long-range translational diffusion of water. The cross-relaxation rates, analyzed in the framework of a model (Nordstierna, L.; Yushmanov, P. V.; Furó, I. J. Chem. Phys. 2006, 125, 074704), provide information about the dynamic retardation of water molecules by the micellar headgroup region and the location of the various moieties along the hydrophobic tail with respect to the water-micelle interface. Both intermolecular cross-relaxation and aggregation-induced 19F chemical shift changes indicate no direct water contact to fluorines except for those closest to the head group.
Nordstierna
Lars
L
Division of Physical Chemistry and Industrial NMR Center, Department of Chemistry, Royal Institute of Technology, SE-10044 Stockholm, Sweden.
Yushmanov
Pavel V
PV
Furó
István
I